Metal azo pigments

ABSTRACT

The novel yellow metal azo pigments based on at least three metal azo compounds which differ at least in the type of metal have improved color strengths and are of excellent suitability for pigmentation of pigment preparations for a broad field of use.

The present invention relates to novel yellow metal azo pigments basedon at least three metal azo compounds which differ at least in the typeof metal, to processes for production thereof and to the use thereof asyellow pigment in pigment preparations.

BACKGROUND INFORMATION

The preparation of metal complexes from azobarbituric acid with nickelsalts and the use thereof as yellow pigments has long been known and hasbeen described many times in the literature (cf., for example, W.Herbst, K. Hunger: Industrial Organic Pigments, 3rd edition 2004, p.390/397). It is additionally known that these products can be reactedfurther, for example with melamine or melamine derivatives, in order toimprove the performance properties of the pigments, for example in thecolouring of plastics, lacquers and colour filters for LCDs.

In addition, the literature states that colouristic properties can alsobe adjusted using, apart from nickel salts, one or more salts ofdifferent metals as well. The application EP-A 1 591 489 describes metalcomplexes of azo compounds containing, as metals, those from the groupof the alkali metals, alkaline earth metals, the lanthanoids, andaluminium, scandium, titanium, vanadium, chromium, manganese, cobalt,copper, nickel and zinc, and optionally iron. The pigments obtained havea different colour locus compared to the pure nickel-azobarbituric acidcomplexes.

Controlled surface coverage of the metal azo pigment can likewiseachieve an improvement in performance-based properties, specifically thelowering of the dispersion hardness as a measure of the dispersionproperties of the pigment. However, this method of improvingdispersibility is associated with a reduction in the colour intensity ofthe pigment, which is directly dependent on the concentration ofcovering agent.

A further means of adjusting performance-based properties is to subjectthe pigments produced from nickel-azobarbituric acid complexes withmelamine, for example, to a heat treatment. This process step isassociated with a controlled alteration in the particle size of thepigments and the specific surface area thereof. This process isdescribed, for example, in EP-A 0 994 162.

The metal azo pigments known from the prior art are still in need ofimprovement with regard to the performance features thereof.

SUMMARY OF THE INVENTION

It has been found that metal azo pigments based on azobarbituric acid,nickel salts, copper salts and melamine and/or melamine derivatives andat least one further metal salt other than nickel salts surprisinglyhave improved dispersion properties with a simultaneous increase in thecolour intensity. The improvement of these properties enables improveduse of these products, inter alia, for colouring of plastics andlacquers, and for use in inkjets and as a component of colour filtersfor LCDs.

DESCRIPTION OF THE EMBODIMENTS

The invention therefore relates to metal azo pigments, characterized inthat they comprise the following components:

-   a) at least three metal azo compounds which differ at least in the    type of metal and which each contain    -   structural units of the formula (I), or the tautomeric forms        thereof,

-   -   -   in which

    -   R¹ and R² are each independently OH, NH₂ or NHR⁵,

    -   R³ and R⁴ are each independently ═O or ═NR⁵,

    -   R⁵ is hydrogen or alkyl, preferably C₁-C₄-alkyl,

    -   and

    -   Ni²⁺ and/or Cu²⁺ ions and at least one further metal ion ME,

    -   where

    -   Me is a di- or trivalent metal ion selected from the group of        La³⁺, Ce³⁺, Pr³⁺, Nd²⁺, Nd³⁺, Sm²⁺, Sm³⁺, Eu²⁺, Eu³⁺, Gd²⁺,        Tb³⁺, Dy³⁺, Ho³⁺, Yb²⁺, Yb³⁺, Er³⁺, Tm³⁺, Ca²⁺, Sr²⁺, Mn²⁺, Y³⁺,        Sc³⁺, Ti²⁺, Ti³⁺, Nb³⁺, Mo³⁺, V²⁺, V³⁺, Zr²⁺, Zr³⁺, Cd²⁺, Cr³⁺,        Pb²⁺ and Ba²⁺,

    -   with the proviso that the amount of Cu²⁺ and Ni²⁺ ions together        is 70 to 99.5 mol % and the amount of metal ions Me is 30 to 0.5        mol %, based in each case on one mole of all metal ions in the        metal azo pigment,

    -   and

    -   where the molar ratio of Cu²⁺ to Ni²⁺ ions in the metal azo        pigment is 42:1 to 1:42, preferably 10:1 to 1:10 and more        preferably 3:1 to 1:3,

    -   and

-   b) at least one compound of the formula (II)

-   -   in which    -   R⁶ is hydrogen or alkyl, preferably C₁-C₄-alkyl optionally mono-        or polysubstituted by OH.

Preferably, in formula (I), R¹ and R² are each independently OH, NH₂ oran NHR⁵ radical where R⁵ is hydrogen or C₁-C₄-alkyl.

Preferably, in formula (I), R³ and R⁴ are each independently ═O or ═NR⁶where R⁵ is hydrogen or C₁-C₄-alkyl.

More preferably, in formula (I), R¹ and R² are OH and R³ and R⁴ are ═O.

Preferably, in formula (II), R⁶ is hydrogen or C₁-C₄ alkyl optionallymono- or polysubstituted by OH. More preferably, in formula (II), R⁶ ishydrogen.

Based on one more of all metal ions present in the metal azo pigment,the amount of Cu²⁺ and Ni²⁺ ions together is generally 70 to 993 mol %and the amount of metal ions Me 30 to 0.5 mol %; the amount of Cu²⁺ andNi²⁺ ions together is preferably 75 to 95 mol % and the amount of metalions Me 25 to 5 mol %, and the amount of Cu²⁺ and Ni²⁺ ions together ismore preferably 80 to 90 mol % and the amount of metal ions Me 20 to 10mol %.

The molar ratio of Cu²⁺ to Ni²⁺ ions in the metal azo pigment isgenerally 42:1 to 1:42, preferably 10:1 to 1:10 and more preferably 3:1to 1:3.

Substituents in the definition of alkyl denote, for example,straight-chain or branched C₁-C₆-alkyl, preferably straight-chain orbranched C₁-C₄-alkyl, which may optionally be mono- or polysubstitutedidentically or differently, for example by halogen such as chlorine,bromine or fluorine; —OH, —CN, —NH₂ or C₁-C₆-alkoxy.

Said metal ions Me are preferably in their most stable oxidation states.

In general, Me is a di- or trivalent metal ion selected from the groupof La³⁺, Ce³⁺, Pr³⁺, Nd²⁺, Nd³⁺, Sm²⁺, Sm³⁺, Eu²⁺, Eu³⁺, Tb³⁺, Dy³⁺,Ho³⁺, Yb²⁺, Yb³⁺, Er³⁺, Tm³⁺, Mg²⁺, Ca²⁺, Sr²⁺, Mn²⁺, Y³⁺, Sc³⁺, Ti²⁺,Ti³⁺, Nb³⁺, Mo²⁺, Mo³⁺, V²⁺, V³⁺, Zr²⁺, Zr³⁺, Cd²⁺, Cr³⁺, Pb²⁺ and Ba²⁺.Preferably, Me is a di- or trivalent metal ion selected from the groupof La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm⁺, Eu³⁺, Gd³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Yb³⁺,Er³⁺, Tm³⁺, Mg²⁺, Ca²⁺, Sr³⁺, Mn²⁺ and Y³⁺ and more preferably from thegroup of La³⁺, Ce³⁺, Pr²⁺, Nd³⁺, Sm³⁺, Tb³⁺, Ho³⁺ and Sr²⁺.

In the case that the metal azo compounds of component a) containdivalent metal ions ME, the structural units of the formula (I) and themetal ions Me can be regarded as complexes, for example those of theformula (Ia)

However, it is also possible that the metal ion is bonded via thenitrogen atoms in a tautomeric notation of the formula (Ia).

The same formula representation can be applied to the structural unitsof the formula (I) with the Cu²⁺ ions or with the Ni²⁺ ions. Thisrepresentation serves merely for illustration and does not make anyclaim to scientific correctness.

In the case that Me is a trivalent metal ion, the charge is balancedpreferably by an equivalent amount of anionic structural units of theformula (I).

Preferably, the charge of the doubly negatively charged structural unitsof the formula (I) is balanced to an extent of 80% to 100%, morepreferably to an extent of 95% to 100% and most preferably to an extentof 99.9% to 100% by the sum total of all Cu²⁺ and Ni²⁺ present in themetal azo pigment and further metal ions Me.

Preferably, the said metal azo compounds of components a) form adductswith components b), i.e. the compounds of the formula (II).

Adducts are understood here to mean molecular assemblies in general. Thebond between the molecules here may be the result, for example, ofintermolecular interactions or Lewis acid-base interactions or ofcoordinate bonds.

The term “adduct” in the context of the present invention shallgenerally encompass all kinds of intercalation and addition compounds.

The terms “intercalation compound” or “addition compound” in the contextof the present invention shall be understood, for example, to meancompounds which are formed on the basis of intermolecular interactionssuch as van der Waals interactions or else Lewis acid-base interactions.The way in which the intercalation proceeds here depends both on thechemical properties of the component to be intercalated and on thechemical nature of the host lattice. Compounds of this kind arefrequently also referred to as intercalation compounds. In a chemicalsense, this is understood to mean the intercalation of molecules andions (less commonly atoms as well) into chemical compounds.

This shall additionally also be understood to mean inclusion compoundscalled clathrates. These are compounds of two substances, one of whichis a guest molecule intercalated into a lattice or cage composed of ahost molecule.

The terms “intercalation compound” or “addition compound” in the contextof the present invention shall also be understood to mean mixedintercalation crystals (including interstitial compounds). These arechemical non-stoichiometric crystalline compounds composed of at leasttwo elements.

In addition, the terms “intercalation compound” or “addition compound”in the context of the present invention shah also be understood to meancompounds which are formed on the basis of coordinate bonds or complexbonds. Compounds of this kind refer, for example, to mixed substitutioncrystals or mixed replacement crystals in which at least two substancesform a common crystal and the atoms of the second component are atregular lattice sites of the first component.

Preference is given to metal azo pigments comprising the adducts of

-   -   a) at least three metal azo compounds which differ at least in        the type of metal and which each contain structural units of the        above-specified formula (I)        -   in which R¹ and R² are OH,        -   and        -   R³ and R⁴ are ═O,        -   and        -   Ni²⁺ and/or Cu²⁺ ions and at least one further metal ion Me,        -   where        -   Me is a di- or trivalent metal ion selected from the group            of La³⁺, Ce³⁺, Pr²⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Tb³⁺, Dy³⁺,            Ho³⁺, Yb³⁺, Er³⁺, Tm³⁺, Mg²⁺, Ca²⁺, Sr²⁺, Mn²⁺ and Y³⁺.        -   with the proviso that the amount of Cu²⁺ and Ni²⁺ ions            together is 70 to 99.5 mol % and the amount of metal ions Me            is 30 to 0.5 mol %, based in each case on one mole of all            metal) ions in the metal azo pigment,        -   and        -   where the molar ratio of Cu²⁺ to Ni²⁺ ions in the metal azo            pigment is 42:1 to 1:42, preferably 10:1 to 1:10 and more            preferably 3:1 to 1:3,        -   and    -   b) at least one compound of the above-specified formula (II)        -   in which        -   R⁶ is hydrogen.

Particular preference is given to metal azo pigments comprising theadducts of

-   -   a) at least three metal azo compounds which differ at least in        the type of metal and which each contain structural units of the        above-specified formula (I)        -   to in which R¹ and R² are OH,        -   and        -   R³ and R⁴ are ═O        -   and        -   Ni²⁺ and/or Cu²⁺ ions and at least one further metal ion Me,        -   where        -   Me is a di- or trivalent metal ion selected from the group            of La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Tb³⁺, Ho³⁺ and Sr²⁺,        -   with the proviso that the amount of Cu²⁺ and Ni²⁺ ions            together is 70 to 99.5 mol % and the amount of metal ions Me            is 30 to 0.5 mol %, based in each case on one mole of all            metal ions in the metal azo pigment,        -   and        -   where the molar ratio of Cu²⁺ to Ni²⁺ ions in the metal azo            pigment is 42:1 to 1:42, preferably 10:1 to 1:10 and more            preferably 3:1 to 1:3,        -   and    -   b) at/east one compound of the above-specified formula (II)        -   in which        -   R⁶ is hydrogen.

Compounds suitable for forming an adduct in the sense of the abovedefinition with the metal azo compounds of component a) may be eitherorganic or inorganic compounds. These compounds are referred tohereinafter as adduct formers.

Adduct formers suitable in principle come from an extremely wide varietyof different compound classes. For purely practical reasons, preferenceis given to those compounds which are solid or liquid under standardconditions (25° C., 1 bar).

Among the liquid substances, preference is generally given to thosehaving a boiling point of 100° C. or higher, preferably of greater thanor equal to 150° C. at 1 bar. Suitable adduct formers are generallyacyclic and cyclic organic compounds, for example aliphatic and aromatichydrocarbons which may be substituted, for example, by OH, COOH, NH₂,substituted NH₂, CONH₂, substituted CONH₂, SO₂NH₂, substituted SO₂NH₂,SO₃H, halogen, NO₂, CN, —SO₂-alkyl, —SO₂-aryl, —O-alkyl, —O-aryl,—O-acyl.

Carboxamides and sulphonamides are a preferred group of adduct formers;also especially suitable are urea and substituted ureas such asphenylurea, dodecylurea and others, and the polycondensates thereof withaldehydes, especially formaldehyde; heterocycles such as barbituricacid, benzimidazolone, benzimidazolone-5-sulphonic add,2,3-dihydroxyquinoxaline, 2,3-dihydroxyquinoxaline-6-sulphonic add,carbazole, carbazole-3,6-disulphonic add, 2-hydroxyquinoline,2,4-dihydroxyquinoline, caprolactam, melamine,6-phenyl-1,3,5-triazine-2,4-diamine,6-methyl-1,3,5-triazine-2,4-diamine, cyanuric acid.

Likewise suitable in principle as adduct formers are polymers,preferably water-soluble polymers, for example ethylene-propylene oxideblock polymers, preferably having an M_(n) greater than or equal to1000, especially from 1000 to 10 000 g/mol, polyvinyl alcohol,poly(meth)acrylic adds, modified cellulose such as carboxymethylcellulases, hydroxyethyl and -propyl celluloses, methyl and ethylhydroxyethyl celluloses.

According to the invention, the adduct formers used are those of theformula (II). Especially preferred here is melamine.

In general, the metal azo pigments of the invention contain 0.05 to 4mol, preferably 0.5 to as mol and most preferably 1.0 to 2.0 mol ofcompounds of the formula (II) per mole of structural units of theformula (I).

The metal azo pigments of the invention preferably have a specificsurface area (m²/g) of 50 to 200 m²/g, especially 80 to 160 m²/g, mostpreferably 100 to 150 m²/g. The surface area is determined in accordancewith DIN 66131: determination of the specific surface area of solids bygas adsorption according to Brunauer, Emmett and Teller (B.E.T).

The metal azo pigments of the invention may be physical mixtures orchemical mixed compounds.

Preferably, the physical mixtures are mixtures of adducts of said metalazo compounds of component a) and the compounds of the formula (II) ofcomponent b) which differ at least in terms of the type of metals.Preferred examples are the physical mixture of the adducts of a1) thepure Ni azo compound with b1) melamine and the adducts of a2) the pureCu azo compound with b2) melamine and the adducts of a3) with at leastone further Me azo compound with b3) melamine.

The chemical mixed compounds are, for example and with preference,adducts of metal azo compounds of component a) with compounds of theformula (II) of component b), preferably melamine, where the Ni²⁺ andCu²⁺ ions, and any further metal ion Me, are incorporated into a commoncrystal lattice.

In the case of the present invention, there is no difference in thex-ray diffractograms of the physical mixtures and the chemical mixedcompounds.

The metal azo pigments of the invention are notable for characteristicsignals in the x-ray diffractogram. Especially in that, in the x-raydiffractogram, at an interplanar spacing of d=12.2 (±0.2) Å, the metalazo pigment has a signal S₁ having an intensity I₁ which exceeds thebackground value by 3 times the square root of this value. Thesecharacteristic signals occur especially in the case of the metal azopigments of the invention where the amount of Cu²⁺ and Ni²⁺ ionstogether is 80 to 90 mol % and the amount of metal ions Me is 10 to 20mol %.

The meta azo pigments of the invention can be prepared by reactingalkali metal salts of the formula (III), or tautomers thereof,preferably the sodium or potassium salts, in the presence of at leastone compound of the formula (II) with nickel and copper salts and one ormore metal salts from the group of the lanthanum, cerium, praseodymium,neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium,ytterbium, erbium, thulium, magnesium, calcium, strontium, manganese,yttrium, scandium, titanium, niobium, molybdenum, vanadium, zirconium,cadmium, chromium, lead and barium salts, preferably from the group ofthe lanthanum, cerium, praseodymium, neodymium, samarium, europium,gadolinium, terbium, dysprosium, holmium, ytterbium, erbium, thulium,magnesium, calcium, strontium, manganese and yttrium salts, and morepreferably from the group of the lanthanum, cerium, praseodymium,neodymium, samarium, terbium, holmium and strontium salts.

The metal azo pigments of the invention can also be prepared by mixingthe adducts of a1) metal azo compounds containing structural units ofthe formula (I) and Ni²⁺ ions and b1) compounds of the formula (II) withadducts of a2) metal azo compounds containing structural units of theformula (I) and Cu²⁺ ions and b2) compounds of formula (II) with adductsof a3) metal azo compounds containing structural units of the formula(I) and metal ions Me and b3) compounds of the formula (II).

The present invention further provides a process for producing the metalazo pigments of the invention, which is characterized in that at leastone compound of the formula (III), or tautomers thereof,

-   -   in which    -   X is an alkali metal ion, preferably a sodium or potassium ion,    -   R¹ and R² are each independently OH, NH₂ or NHR⁵,    -   R³ and R⁴ are each independently ═O or ═NR⁵,    -   and    -   R⁵ is hydrogen or alkyl, preferably C₁-C₄-alkyl,        in the presence of at least one compound of the formula (II), is        reacted simultaneously or successively with at least one nickel        salt and at least one copper salt and with at least one further        metal salt from the group of the La³⁺, Ce³⁺, Pr³⁺, Nd²⁺, Nd³⁺,        Sm²⁺, Sm³⁺, Eu²⁺, Eu³⁺, Gd³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Yb²⁺, Yb³⁺,        Er³⁺, Tm³⁺, Mg²⁺, Ca²⁺, Sr²⁺, Mn²⁺, Y³⁺, Sc³⁺, Ti²⁺, Ti³⁺, Nb³⁺,        Mo²⁺, Mo³⁺, V²⁺, V³⁺, Zr²⁺, Zr³⁺, Cd²⁺, Cr³⁺, Pb²⁺ and Ba²⁺        salts, preferably from the group of the La³⁺, Ce²⁺, Pr³⁺, Nd³⁺,        Sm³⁺, Eu³⁺, Gd³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Yb³⁺, Er³⁺, Tm³⁺, Mg²⁺,        Ca²⁺, Sr²⁺, Mn²⁺ and Y³⁺ salts and more preferably from the        group of La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Tb³⁺, Ho³⁺ and Sr³⁺        salts, where 0.02 to 0.96 mol of at least one nickel salt, 0.02        to 0.96 mol of at least one copper salt and 0.005 to 0.3 mol of        at least one further metal salt from the abovementioned group of        the metal salts are used per mole of compound of the formula        (III), and the sum total of the molar amounts of all these metal        salts together is one mole.

Preferably, 0.05 to 0.9 mol of at least one nickel salt and 0.05 to 0.9mol of at least one copper salt and 0.05 to 025 mol of at least onefurther metal salt from the abovementioned group are used per mole ofcompound of the formula (III).

Most preferably, 0.2 to 0.6 mol of at least one nickel salt and 0.2 to0.6 mol of at least one copper salt and 0.07 to 0.2 mol of at least onefurther metal salt from the abovementioned group are used per mole ofcompound of the formula (III).

In general, the process of the invention is performed using 0.05 to 4mol, preferably 0.5 to 2.5 mol and most preferably 1.0 to 2.0 mol ofcompound of the formula (II) per mole of compound of the formula (III).

Alternatively, for the preparation, instead of the di-alkali metalcompound of the formula (III), it is also possible to use a mono-alkalimetal compound of the formula (IIIa), or tautomers thereof,

-   -   in which X, R¹, R², R³ and R⁴ have the definition given for        formula (III),        or a mixture of compounds of the formula (III) and (IIIa). The        stated molar amounts of nickel and copper salts and the further        metal salts from the abovementioned group and of compounds of        the formula (II) in these cases relate to the sum total of the        molar amounts of the compounds (III) and (IIIa) used.

The process of the invention is generally conducted at a temperature of60 to 95° C. in aqueous solution at a pH below 7. The nickel and coppersalts for use in accordance with the invention and the further metalsalts from the abovementioned group can be used individually or as amixture with one another, preferably in the form of an aqueous solution.The compounds of the formula (II) may likewise be added individually oras a mixture with one another, preferably in the form of the solids.

In general, the process of the invention is conducted in such a way thatthe am compound of the formula (III), preferably as the sodium orpotassium salt, is initially charged, one or more compounds of theformula (II), preferably melamine, is/are added and then reaction iseffected successively or simultaneously with at least one nickel saltand at least one copper salt and one or more metal salts from theabove-specified group, preferably in the form of the aqueous solutionsof these salts, preferably at pH values less than 7. Suitable substancesfor adjusting the pH are sodium hydroxide solution, potassium hydroxidesolution, sodium carbonate, sodium hydrogencarbonate, potassiumcarbonate and potassium hydrogencarbonate.

Useful nickel and copper salts preferably include the water-solublesalts thereof, especially chlorides, bromides, acetates, formates,nitrates, sulphates, etc. Nickel and copper salts used with preferencehave a water solubility of more than 20 g/l, especially more than 50g/l, at 20° C.

Useful further metal salts from the group of the lanthanum, cerium,praseodymium, neodymium, samarium, europium, gadolinium, terbium,dysprosium, holmium, ytterbium, erbium, thulium, magnesium, calcium,strontium, manganese, yttrium, scandium, titanium, niobium, molybdenum,vanadium, zirconium, cadmium, chromium, lead and barium salts preferablyinclude the water-soluble salts thereof, especially the chlorides,bromides, acetates, nitrates and sulphates thereof, preferably thechlorides thereof.

The metal azo pigments of the invention obtained in this way can then beisolated by filtration of the aqueous suspensions thereof as an aqueousfiltercake. This filtercake, optionally after washing with hot water,can be dried by means of standard drying methods.

Useful drying methods include, for example, paddle drying or spraydrying of corresponding aqueous slurries.

Subsequently, the pigment can be reground.

If the metal azo pigments of the invention have excessively hard grainsor are too hard to be dispersed for the desired application, they can beconverted to soft-grained pigments, for example by the method describedin DE-A 19 847 586.

The present invention further provides a process for producing the metalazo pigments of the invention, which is characterized in that

-   -   (i) at least one adduct of        -   a1) a metal azo compound containing structural units of the            above-specified formula (I)        -   in which        -   R¹, R², R³, R⁴ and R⁵ have the above-specified general and            preferred definition,        -   and        -   Cu²⁺ ions,        -   and        -   b1) at leas/one compound of the above-specified formula (II)            in which R⁶ has the general and preferred definitions given            above,        -   and the amount of Cu²⁺ metal ions is 100 mol %, based on one            mole of all metal ions in the adduct a1)/b1),        -   with    -   (ii) at least one adduct of        -   a2) a metal azo compound containing structural units of the            above-specified formula (I)        -   in which        -   R¹, R², R³, R⁴ and R⁵ have the above-specified general and            preferred definition,        -   and    -   Ni²⁺ ions,    -   and        -   b2) at least one compound of the above-specified            formula (II) in which R⁶ has the general and preferred            definitions given above,    -   and the amount of Ni²⁺ metal ions is 100 mol %, based on one        mole of all metal ions in the adduct a2)/b2),    -   and    -   (iii) at least one adduct of        -   a3) a metal azo compound containing structural units of the            above-specified formula (I)    -   in which    -   R¹, R², R³, R⁴ and R⁵ have the above-specified general and        preferred definition,    -   and    -   at least one metal ion Me,    -   where    -   Me is a di- or trivalent metal ion selected from the group of        La³⁺, Ce³⁺, Pr³⁺, Nd³⁺, Nd³⁺, Sm²⁺, Sm²⁺, Eu²⁺, Eu³⁺, Gd³⁺,        Tb³⁺, Dy³⁺, Ho³⁺, Yb²⁺, Yb³⁺, Er³⁺, Tm²⁺, Mg²⁺, Ca²⁺, Sr²⁺,        Mn²⁺, Y³⁺, Sc³⁺, Ti²⁺, Ti³⁺, Nb³⁺, Mo²⁺, Mo³⁺, V²⁺, V³⁺, Zr²⁺,        Zr³⁺, Cd³⁺, Cr³⁺, Pb²⁺ and Ba²⁺,    -   and        -   b3) at least one compound of the above-specified            formula (II) in which R⁶ has the general and preferred            definitions given above,            -   and the amount of Me metal ions is 100 mol %, based on                one mole of all metal ions in the adduct a3)/b3),                are mixed with one another, where 0.02 to 42 mol of                adduct a2)/b2) are used and 0005 to 0.42 mol of adduct                a3)/b3) are used per mole of adduct a1)/b1), based on                the sum total of the molar amount of adducts a1)/b1) and                a2)/b2).

The metal azo pigments of the invention are notable for particularlygood dispersibility and a high colour intensity. Chrome and transparencyhave excellent adjustability.

The metal azo pigments of the invention are of excellent suitability forall pigment applications, especially also in the form of the pigmentpreparations thereof.

The present invention further provides pigment preparations comprisingat least one metal azo pigment of the invention and at least oneauxiliary and/or additive.

Useful auxiliaries or additives generally include all additions that arecustomary for pigment preparations, for example those from the group ofthe surface-active agents such as dispersants, surfactants, wettingagents, emulsifiers, and those from the group of the surface-coveringagents, bases and solvents. In principle, the auxiliary or additive isguided by the nature of the target system. If the target system is, forexample, a lacquer or a printing ink, the auxiliary or additive is thenselected so as to achieve maximum compatibility with the target system.

Preferably, the pigment preparations of the invention comprise at leastone surface-active agent.

Surface-active agents in the context of the present invention areespecially understood to mean dispersants, which stabilize the pigmentparticles in their fine particulate form in aqueous media. “Fineparticulate” is preferably understood to mean a fine distribution of0.001 to 5 μm, especially of 0.005 to 1 μm, more preferably of 0.005 to0.5 μm. The pigment preparation of the invention is preferably in fineparticulate form.

Suitable surface-active agents are, for example, anionic, cationic,amphoteric or nonionic in nature.

Suitable anionic surface-active agents (c) are especially condensationproducts of aromatic sulphonic acids with formaldehyde, such ascondensation products of formaldehyde and alkylnaphthalenesulphonicacids or of formaldehyde, naphthalenesulphonic acids and/orbenzenesulphonic acids, condensation products of optionally substitutedphenol with formaldehyde and sodium bisulphite. Also suitable aresurface-active agents from the group of the sulphosuccinic esters andalkylbenzenesulphonates. Also ionically modified, especially sulphatedor carboxylated, alkoxylated fatty acid alcohols or salts thereof.Alkoxylated fatty acid alcohols are especially understood to mean thoseC₆-C₂₂ alcohols endowed with 5 to 120, preferably 5 to 60 and especiallywith 5 to 30 ethylene oxide, which are saturated or unsaturated.Additionally useful are lignosulphonates in particular, for examplethose which are obtained by the sulphite or Kraft process. They arepreferably products which are partially hydrolysed, oxidized,propoxylated, sulphonated, sulphomethylated or desulphonated and whichare fractionated by known methods, for example according to themolecular weight or the degree of sulphonation. Mixtures of sulphite andKraft lignosulphonates are also very effective. Especially suitable arelignosulphonates with an average molecular weight between 1000 and 100000 g/mol, a content of active lignosulphonate of at least 80% by weightand, preferably, a low content of polyvalent cations. The degree ofsulphonation can be varied within wide limits.

Examples of useful nonionic surface-active agents include: reactionproducts of alkylene oxides with compounds capable of being alkylated,such as, for example, fatty alcohols, fatty amines, fatty acids,phenols, alkylphenols, arylalkylphenols, such as styrene-phenolcondensates, carboxamides and resin acids. These are, for example,ethylene oxide adducts from the class of the reaction products ofethylene oxide with:

1) saturated and/or unsaturated fatty alcohols having 6 to 22 carbonatoms or

2) alkylphenols having 4 to 12 carbon atoms in the alkyl radical or

3) saturated and/or unsaturated fatty amines having 14 to 20 carbonatoms or

4) saturated and/or unsaturated fatty acids having 14 to 20 carbon atomsor

5) hydrogenated and/or unhydrogenated resin acids.

Useful ethylene oxide adducts especially include the alkylatablecompounds mentioned in 1) to 5) having 5 to 120, especially 5 to 100,especially 5 to 60 and more preferably 5 to 30 mol of ethylene oxide.

Suitable surface-active agents are likewise the esters of thealkoxylation product of the formula (X) that are known from DE-A 19 712486 or from DE-A 19 535 246, which correspond to the formula (XI), andthe latter optionally in a mixture with the parent compounds

of the formula (X). The alkoxylation product of a styrene-phenolcondensate of the formula (X) is as defined below:

-   in which-   R¹⁵ is hydrogen or C₁-C₄-alkyl,-   R¹⁶ is hydrogen or CH₃,-   R¹⁷ is hydrogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or    phenyl,-   m is a number from 1 to 4,-   n is a number from 6 to 120,-   R¹⁸ is the same or different for every unit indicated by n and is    hydrogen, CH₃ or phenyl, where, in the case that CH₃ is present in    some of the different —(—CH₂—CH(R¹⁸)—O—) groups, R¹⁸ is CH₃ in 0% to    60% of the total value of n and R¹⁸ is hydrogen in 100% to 40% of    the total value of n, and where, in the case that phenyl is present    in some of the different —(—CH₂—CH(R¹⁸)—O—) groups, R¹⁸ is phenyl in    0% to 40% of the total value of n and R¹⁸ is hydrogen in 100% to 60%    of the total value of n.

The esters of the alkoxylation products (X) correspond to the formula(XI)

-   In which-   R^(15′), R^(16′), R^(17′), R^(18′), m′ and n′ assume the scope of    the definition of R¹⁵, R¹⁶, R¹⁷, R¹⁸, m and n, but independently    thereof,-   X is the —SO₃, —SO₂, —PO₃ or —CO—(R¹⁹)—COO group,-   Kat is a cation from the group of H, Li, Na, K, NH₄ or    HO—CH₂CH₂—NH₃, where two Kat are present in the case that X═—PO₃,    and-   R¹⁹ is a divalent aliphatic or aromatic radical, preferably    C₁-C₄-alkylene, especially ethylene, C₂-C₄ monounsaturated radicals,    especially acetylene or optionally substituted phenylene, especially    ortho-phenylene, where possible substituents preferably include    C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl or phenyl.

A preferred surface-active agent used is the compound of the formula(XI). Preferably a compound of the formula (XI) in which X is a radicalof the formula —CO—(R¹⁹)—COO⁻ and R¹⁹ is as defined above.

Preference is likewise given to using, as surface-active agent, acompound of the formula (XI) together with a compound of the formula,(X). Preferably, the surface-active agent in this case contains 5% to99% by weight of the compound (XI) and 1% to 95% by weight of thecompound (X).

The surface-active agent of component (c) is preferably used in thepigment preparation in an amount of 0.1% to 100% by weight, especially0.5% to 80% by weight, based on the metal azo pigment of the inventionused.

It will be appreciated that the pigment preparation of the invention mayalso contain further additions. For example, additions which lower theviscosity of an aqueous suspension and/or increase the solids content,for example carboxamides and sulphonamides, may be added in an amount ofup to 10% by weight, based on the pigment preparation.

Further additions are, for example, inorganic and organic bases, andadditions customary for pigment preparations.

Bases include: alkali metal hydroxides, for example NaOH, KOH or organicamines such as alkylamines, especially alkanolamines oralkylalkanolamines.

Particularly preferred examples include methylamine, dimethylamine,trimethylamine, ethanolamine, n-propanolamine, n-butanolamine,diethanolamine, triethanolamine, methylethanolamine ordimethylethanolamine.

Examples of suitable carboxamides and sulphonamides include: urea andsubstituted ureas such as phenylurea, dodecylurea and others;heterocycles such as barbituric acid, benzimidazolone,benzimidazolone-5-sulphonic acid, 2,3-dihydroxyquinoxaline,2,3-dihydroxyquinoxaline-6-sulphonic acid, carbazole,carbazole-3,6-disulphonic acid, 2-hydroxyquinoline,2,4-dihydroxyquinoline, caprolactam, melamine,6-phenyl-1,3,5-triazine-2,4-diamine,6-methyl-1,3,5-triazine-2,4-diamine, cyanuric acid.

The base is optionally present up to an amount of 20% by weight,preferably up to 10% by weight, based on the pigment.

In addition, the pigment preparations of the invention may still containinorganic and/or organic salts as a result of the preparation.

The pigment preparations of the invention are preferably solid at roomtemperature. More particularly, the pigment preparations of theinvention are in the form of powders or granules.

The pigment preparations of the invention are of excellent suitabilityfor all pigment applications.

The present invention further provides for the use of at least one metalazo pigment of the invention or of a pigment preparation of theinvention for pigmentation of all kinds of lacquers for the productionof printing inks, distempers or emulsion paints, for the bulk colouringof paper, for the bulk colouring of synthetic, semisynthetic or naturalmacromolecular substances, for example polyvinyl chloride, polystyrene,polyamide, polyethylene or polypropylene. They can also be used for thespin dyeing of natural, regenerated or synthetic fibres, for examplecellulose, polyester, polycarbonate, polyacrylonitrile or polyamidefibres, and for printing of textiles and paper. These pigments can beused to produce finely divided, stable, aqueous pigmentations foremulsion paints and other paints usable for paper colouring, for thepigment printing of textiles, for laminate printing or for the spindyeing of viscose, by grinding or kneading in the presence of nonionic,anionic or cationic surfactants.

The metal azo pigments of the invention are additionally of excellentsuitability for inkjet applications and for colour filters forliquid-crystal displays.

In a likewise preferred embodiment, the pigment preparations of theinvention comprise at least one organic compound (d) selected from thegroup of the terpenes, terpenoids, fatty acids, fatty acid esters andthe homo- or copolymers, such as random or block copolymers having asolubility in pH-neutral water at 20° C. of less than 1 g/l, especiallyless than 0.1 g/l. The organic compound (d) is preferably solid orliquid at room temperature (0° C.) under standard atmosphere and, if itis liquid, has a boiling point of preferably >100° C., especially >150°C.

Preferred polymers have both a hydrophilic and a hydrophobic, preferablypolymeric, molecular moiety. Examples of such polymers are randomcopolymers based on fatty acids or long-chain C₁₂-C₂₂ hydrocarbons andpolyalkylene glycols, especially polyethylene glycol. Also blockcopolymers based on (poly)hydroxy fatty adds and polyalkylene glycol,especially polyethylene glycol, and also graft copolymers based onpoly(meth)acrylate and polyalkylene glycol, especially polyethyleneglycol.

Preferred compounds from the group of the terpenes, terpenoids, fattyadds and fatty add esters include: ocimene, myrcene, geraniol, nerd,linalool, citronellol, geranial, citronellal, neral, limonene, menthol,for example (−)-menthol, menthone or bicyclic monoterpenes, saturatedand unsaturated fatty adds having 6 to 22 carbon atoms, for exampleoleic add, linoleic add and linolenic add or mixtures thereof.

Also useful as organic compounds of component (d) are the abovementionedadduct formers, provided that they obey the criteria desired for thecompound of component (d).

Particularly preferred pigment preparations comprise:

-   50%-99% by weight of at least one metal azo pigment of the invention    and-   1%-50% by weight, preferably 2% to 50% by weight of at least one    compound of component (d).

Optionally, the pigment preparation of the invention additionallycomprises a surface-active agent (c).

More preferably, the preparations of the invention consist to an extentof more than 90% by weight, preferably more than 95% by weight andespecially more than 97% by weight of at least one metal azo pigment ofthe invention, at least one organic compound of component (d) andoptionally at least one surface-active agent of component (c) andoptionally at least one base.

The pigment preparations of the invention in this composition areespecially suitable for pigmentation of inkjet inks and colour filtersfor liquid-crystal displays.

The present invention further provides a process for producing thepigment preparations of the invention, which is characterized in that atleast one metal azo pigment of the invention and at least one auxiliaryor additive, especially at least one organic compound of component (d)and optionally at least one surface-active agent of component (c) andoptionally at least one base are mixed with one another.

The present invention likewise provides for the use of the metal azopigments of the invention or of the pigment preparations of theinvention for production of colour filters for liquid-crystal displays.This use will be described hereinafter using the example of the pigmentdispersion method according to the photoresist process.

The inventive use of the pigment preparations of the invention forproduction of colour filters is characterized in that, for example, atleast one metal azo pigment of the invention or a pigment preparation ofthe invention, especially a solid pigment preparation, is homogenized,optionally with a binder resin and an organic solvent, optionally withaddition of a dispersant, and then wet-comminuted continuously orbatchwise to a particle size by number (electron microscopydetermination) of 99.5%<1000 nm, preferably 95%<500 nm and especially90%<200 nm.

Useful wet comminution methods include, for example, stirrer ordissolver dispersion, grinding by means of stirred ball mills or beadmills, kneaders, roll mills, high-pressure homogenization or ultrasounddispersion.

During the dispersion treatment or thereafter, at least one photocurablemonomer and a photoinitiator are added. After the dispersion, it ispossible to introduce further binder resin, solvent, or admixturescustomary for photoresists, as required for the desired photosensitivecoating formulation (photoresist) for production of the colour filters.In the context of this invention, a photoresist is understood to mean apreparation comprising at least one photocurable monomer and aphotoinitiator.

The present invention also provides a process for producing colourfilters for liquid-crystal displays, which is characterized in that atleast one metal azo pigment of the invention or a pigment preparation ofthe invention is homogenized, optionally with a binder resin and anorganic solvent, optionally with addition of a dispersant, and thenwet-comminuted continuously or batchwise to a particle size by number(electron microscopy determination) of 99.5%<1000 nm and, during thedispersion treatment or thereafter, at least one photocurable monomerand a photoinitiator are added.

Useful possible dispersants include dispersants which are suitable forthis application and are generally commercially available, for examplepolymeric, ionic or nonionic dispersants, for example based onpolycarboxylic acids or polysulphonic acids, and also polyethyleneoxide-polypropylene oxide block copolymers. In addition, it is alsopossible to use derivatives of organic dyes as dispersants orco-dispersants.

The production of colour filters therefore gives rise to “formulations”comprising, based on the formulation:

-   -   at least one metal azo pigment of the invention,    -   optionally a binder resin,    -   at least one organic solvent and    -   optionally a dispersant.

In a preferred embodiment, the formulation contains (figures based onformulation):

1%-50% by weight of a metal azo pigment of the invention

0%-20% by weight of binder resin

0%-20% by weight of dispersant

10%-94% by weight of organic solvent.

The coating of the photoresist onto a plate to produce the colouredimage element patterns can be accomplished either by direct or indirectapplication. Examples of application methods include: roller coating,spin coating, spray coating, dip coating and air-knife coating.

Useful plates include, according to the application, for example:transparent glasses such as white or blue glass plates, silicate-coatedblue glass plate, synthetic resin plate or films based, for example, onpolyester resin, polycarbonate resin, acrylic resin or vinyl chlorideresin, and also metal plates based on aluminium, copper, nickel orsteel, and ceramic plates or semiconductor plates having appliedphotoelectric transfer elements.

The application is generally effected such that the layer thickness ofthe photosensitive layer obtained is 0.1 to 10 μm.

The application may be followed by thermal drying of the layer.

The exposure is preferably effected by exposing the photosensitive layerto an active light beam, preferably in the form of an image pattern bymeans of a photomask. This results in curing

of the layer at the exposed sites. Suitable light sources are, forexample: high-pressure and ultrahigh-pressure mercury vapour lamp, xenonlamp, metal halide lamp, fluorescent lamp, and laser beam in the visibleregion.

The development which follows the exposure removes the unexposed portionof the coating and gives the desired image pattern form of the colourelements. Standard development methods include spraying with or dippinginto aqueous alkaline developer solution or into an organic solventcomprising inorganic alkali, for example sodium hydroxide or potassiumhydroxide, sodium metasilicate or organic bases such asmonoethanolamine, diethanolamine, triethanolamine, triethylamine orsalts thereof.

The development is generally followed by a thermal post-drying/curing ofthe image patterns.

The inventive use of the metal azo pigments is preferably characterizedin that they are used alone or in a mixture with other pigments that arecustomary for the production of colour filters in the colour filters orpigment preparations or formulations for colour filters.

These “other pigments” may either be other metal salts of an azocompound of the formula (I) or pigment preparations based thereon orother inorganic or organic pigments.

With regard to the selection of any other pigments to be used as well,there is no restriction in accordance with the invention. Both inorganicand organic pigments are useful.

Preferred organic pigments are, for example, those of the monoazo,disazo, laked azo, β-naphthol, naphthol AS, benzimidazolone, disazocondensations, azo metal complex, isoindoline and isoindolinone series,and also polycyclic pigments, for example from the phthalocyanine,quinacridone, perylene, perinone, thioindigo, anthraquinone, dioxazine,quinophthalone and diketopyrrolopyrroles series. Also laked dyes such asCa, Mg and Al lakes of sulpho- or carboxyl-containing dyes.

Examples of other organic pigments which can optionally be used inaddition are:

Colour Index Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94,109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173,185, or

Colour Index Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61,64, 65, 71, 72, 73 or

Colour Index Pigment Red 9, 97, 122, 123, 144, 149, 166, 168, 177, 180,192, 215, 216, 224, 254, 272, or

Colour Index Pigment Green 7, 10, 36, 37, 45, 58 or

Colour Index Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16 and

Colour Index Pigment Violet 19, 23.

In addition, it is also possible to use soluble organic dyes inconjunction with the novel pigments of the invention.

If “other pigments” are used in addition, the proportion of metal azopigment of the invention is preferably 1%-99% by weight, especially20%-80% by weight, based on the total amount of all pigments used.Particular preference is given to the pigment preparations of theinvention and to formulations comprising at least one metal azo pigmentof the invention and C.I. Pigment Green 36 and/or C.I. Pigment Green 58in a ratio of 20% to 80% by weight of metal azo pigment to 80% to 20% byweight of C.I. Pigment Green 36 and/or C.I. Pigment Green 58, preferablyof 40% to 60% by weight to 60% to 40% by weight.

There is no particular restriction in accordance with the invention withregard to the binder resins which can be used together with the“pigment” or pigment preparations based thereon in colour filters or inthe formulations for production of colour filters, for example by thepigment dispersion method, and useful binder resins are especially thefilm-forming resins known per se for use in colour filters.

For example, useful binder resins include those from the group of thecellulose resins such as carboxymethyl hydroxyethyl cellulose andhydroxyethyl cellulose, acrylic resins, alkyd resins, melamine resins,epoxy resins, polyvinyl alcohols, polyvinylpyrrolidones, polyamides,polyimide imines, polyimides,

polyimide precursors such as those of the formula (14), disclosed inJP-A 11 217 514, and the esterification products thereof.

Examples of these include reaction products of tetracarboxylicdianhydride with diamines.

Useful binder resins also include those which contain photopolymerizableunsaturated bonds. The binder resins may, for example, be those formedfrom the group of acrylic resins. Particular mention should be made hereof homo- and copolymers of polymerizable monomers, for example methyl(meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl(meth)acrylate, styrene and styrene derivatives, and also copolymersbetween carboxyl-bearing polymerizable monomers such as (meth)acrylicacid, itaconic acid, maleic acid, maleic anhydride, monoalkyl maleates,especially with alkyl having 1 to 12 carbon atoms, and polymerizablemonomers such as (meth)acrylic acid, styrene and styrene derivatives,for example α-methylstyrene, m- or p-methoxystyrene, p-hydroxystyrene.Examples include reaction products of carboxyl-containing polymericcompounds with compounds each containing an oxirane ring and anethylenically unsaturated bond, for example glycidyl (meth)acrylate,acryloyl glycidyl ether and itaconic acid monoalkyl glycidyl ether,etc., and also reaction products of carboxyl-containing polymericcompounds with compounds each containing a hydroxyl group and anethylenically unsaturated bond (unsaturated alcohols), such as allylalcohol, 2-buten-4-ol, oleyl alcohol, 2-hydroxyethyl (meth)acrylate,N-methylolacrylamide, etc.:

in addition, such binder resins may also contain unsaturated compoundshaving free isocyanate groups.

In general, the equivalents of unsaturation (molar mass of binder resinper unsaturated compound) of the binder resins mentioned are 200 to3000, especially 230 to 1000, in order to achieve both sufficientphotopolymerizability and hardness of the film. The acid value isgenerally 20 to 300, especially 40 to 200, in order to achievesufficient alkali development capacity after the exposure of the film.

The mean molar mass of the binder resins for use is between 1500 and 200000 and is especially 10 000 to 50 000 g/mol.

The organic solvents used in the inventive use of the pigmentpreparations for colour filters are, for example, ketones, alkyleneglycol ethers, alcohols and aromatic compounds. Examples from the groupof the ketones are: acetone, methyl ethyl ketone, cyclohexanone, etc.;from the group of the alkylene glycol ethers: Methyl Cellosolve(ethylene glycol monomethyl ether), Butyl Cellosolve (ethylene glycolmonobutyl ether), Methyl Cellosolve Acetate, Ethyl Cellosolve Acetate,Butyl Cellosolve Acetate, ethylene glycol monopropyl ether, ethyleneglycol monohexyl ether, ethylene glycol dimethyl ether, diethyleneglycol ethyl ether, diethylene glycol diethyl ether, propylene glycolmonomethyl ether, propylene glycol monoethyl ether, propylene glycolmonopropyl ether, propylene glycol monobutyl ether, propylene glycolmonomethyl ether acetate, diethylene glycol methyl ether acetate,diethylene glycol ethyl ether acetate, diethylene glycol propyl etheracetate, diethylene glycol isopropyl ether acetate, diethylene glycolbutyl ether acetate, diethylene glycol t-butyl ether acetate, Methyleneglycol methyl ether acetate, triethylene glycol ethyl ether acetate,triethylene glycol propyl ether acetate, Methylene glycol isopropylether acetate, triethylene glycol butyl ether acetate, triethyleneglycol t-butyl ether acetate, etc.; from the group of the alcohols:methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 3methyl-3-methoxybutanol, etc.; from the group of the aromatic solvents:benzene, toluene, xylene, N-methyl-2-pyrrolidone, ethylN-hydroxymethyl-2-acetate, etc.

Further other solvents are propane-1,2-diol diacetate,3-methyl-3-methoxybutyl acetate, ethyl acetate, tetrahydrofuran, etc.The solvents may be used individually or in mixtures with one another.

The invention further relates to a photoresist comprising at least onemetal azo pigment of the invention or at least one pigment preparationof the invention and at least one photocurable monomer and at least onephotoinitiator.

The photocurable monomers contain at least one reactive double bond andoptionally other reactive groups in the molecule.

Photocurable monomers are understood in this connection especially tomean reactive solvents or what are cased reactive diluents, for examplefrom the group of the mono-, di-, tri- and multifunctional acrylates andmethacrylates, vinyl ethers and glycidyl ethers. Useful reactive groupsadditionally present include allyl, hydroxyl, phosphate, urethane,secondary amine and N-alkoxymethyl groups.

Monomers of this kind are known to those skilled in the art and aredetailed, for example, in [Römpp Lexikon, Lacke and Druckfarben, Dr.Ulrich Zorll, Thieme Verlag Stuttgart-New York, 1998, p. 491/492].

The selection of monomers is guided especially by the nature andintensity of the radiation type used for the exposure, the desiredreaction with the photoinitiator and the film properties. It is alsopossible to use combinations of monomers.

Photoreaction initiators or photoinitiators are understood to meancompounds which form reactive intermediates as a result of theabsorption of visible or ultraviolet radiation, which can trigger apolymerization reaction, for example of the abovementioned monomersand/or binder resins. Photoreaction initiators are likewise commonlyknown and can likewise be found in [Römpp Lexikon, Lacke rindDruckfarben, Dr. Ulrich Zorll, Thieme Verlag Stuttgart-New York, 1998,p. 445/461].

According to the invention, there is no restriction with regard to thephotocurable monomers or photoinitiators to be used.

The invention preferably relates to photoresists comprising

-   A) at least one metal azo pigment of the invention, especially in a    mixture with other pigments, preferably C.I. Pigment Green 36 and/or    Pigment Green 58 or a pigment preparation of the invention based    thereon,-   B1) at least one photocurable monomer,-   B2) at least one photoinitiator,-   C1) optionally an organic solvent,-   D) optionally a dispersant,-   E) optionally a binder resin,-   and optionally further additions.

According to the invention, there is also no restriction with regard tothe methodology for production of the coloured image element patternsbased on the pigments or solid pigment preparations for use inaccordance with the invention. As well as the above-describedphotolithographic method, other methods such as offset printing,chemical etching or inkjet printing are likewise suitable. The selectionof the suitable binder resins and solvents and of pigment carrier mediaand further additions should be matched to the particular method. In theinkjet method, which is understood to mean both thermal and mechanicaland piezo-mechanical inkjet printing, useful carrier media for thepigments and any binder resins are not only purely organic but alsoaqueous-organic carrier media; aqueous-organic carrier media areactually preferred.

The examples which follow are intended to illustrate the presentinvention but without restricting it thereto.

EXAMPLES

Preparation of the Azobarbituric Acid Precursor (Method 1)

154.1 g of diazobarbituric add and 128.1 g of barbituric add wereintroduced into 3600 g of distilled water at 85° C. Subsequently,aqueous potassium hydroxide solution was used to establish a pH of about5 and the mixture was then stirred for 90 minutes.

Example 1: Preparation of Pigment 1

5000 g of distilled water were added at 82° C. to an azobarbituric acidprepared according to Method 1. Thereafter, 252.2 g of melamine wereintroduced. Subsequently, a mixture of 0.68 mol of an about 30%nickel(II) chloride solution, 0.02 mol of an about 30% copper(II)chloride solution and 0.200 mol of an about 20% lanthanum(III) chloridesolution was added dropwise. After 3 hours at 82° C., KOH was used toestablish a pH of about 5.5. This was followed by dilution at 90° C.with about 1000 g of distilled water. Subsequently, 113 g of 30%hydrochloric add were added dropwise and the mixture was heat-treated at90° C. for 12 hours. Thereafter, aqueous potassium hydroxide solutionwas used to establish a pH of about 5. Subsequently, the pigment wasisolated on a suction filter, washed and dried in a vacuum dryingcabinet at 80° C., and ground in a standard laboratory mill for about 2minutes. (=Pigment 1)

Examples 2 to 144

For preparation of inventive pigments 2 to 100 and of noninventivepigments 101 to 141, the procedure in each case was analogous toExample 1. In each case, 5000 g of distilled water were added at 82° C.to are azobarbituric acid prepared according to Method 1 and then 252.2g of melamine were introduced. Subsequently, rather than the metal saltsolution of Example 1, a metal salt solution as specified in theexamples which follow was added dropwise in each case. The workup andisolation, drying and grinding of the respective pigment in all exampleswere analogous to the method specified in Example 1.

Example 2: Preparation of Pigment 2

A mixture of 0.68 mol of an about 30% nickel(II) chloride solution, 0.02mol of an about 30% copper(II) chloride solution, 0.100 mol of an about20% cerium(III) chloride solution and 0.100 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 3: Preparation of Pigment 3

A mixture of 0.68 mol of an about 30% nickel(II) chloride solution, 0.02mol of an about 30% copper(II) chloride solution, 0.150 mol of an about20% magnesium(II) chloride solution and 0.100 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 4: Preparation of Pigment 4

A mixture of 0.68 mol of an about 30% nickel(II) chloride solution, 0.02mol of an about 30% copper(II) chloride solution, 0.100 mol of an about20% neodymium(III) chloride solution and 0.100 mol of an about 20%gadolinium(III) chloride solution was added dropwise.

Example 5: Preparation of Pigment 5

A mixture of 0.68 mol of an about 30% nickel(II) chloride solution, 0.02mol of an about 30% copper(II) chloride solution, 0.067 mol of an about20% samarium(III) chloride solution, 0.100 mol of an about 20% lead(II)chloride solution and 0.100 mol of an about 20% calcium(II) chloridesolution was added dropwise.

Example 6: Preparation of Pigment 6

A mixture of 0.35 mol of an about 30% nickel(II) chloride solution, 0.35mol of an about 30% copper(II) chloride solution and 0.200 mol of anabout 20% europium(III) chloride solution was added dropwise.

Example 7: Preparation of Pigment 7

A mixture of 0.35 mol of an about 30% nickel(II) chloride solution, 0.35mol of an about 30% copper(II) chloride solution, 0.100 mol of an about20% samarium(III) chloride solution and 0.100 mol of an about 20%gadolinium(III) chloride solution was added dropwise.

Example 8: Preparation of Pigment 8

A mixture of 0.35 mol of an about 30% nickel(II) chloride solution, 0.35mol of an about 30% copper(II) chloride solution, 0.100 mol of an about20% terbium(III) chloride solution and 0.100 mol of an about 20%holmium(III) chloride solution was added dropwise.

Example 9: Preparation of Pigment 9

A mixture of 0.35 mol of an about 30% nickel(II) chloride solution, 035mol of an about 30% copper(II) chloride solution, 0.100 mol of an about20% dysprosium(III) chloride solution and 0.100 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 10: Preparation of Pigment 10

A mixture of 0.35 mol of an about 30% nickel(II) chloride solution, 0.35mol of an about 30% copper(II) chloride solution, 0.067 mol of an about20% holmium(III) chloride solution, 0.067 mol of an about 20%thulium(III) chloride solution and 0.100 mol of an about 20%manganese(II) chloride solution was added dropwise.

Example 11: Preparation of Pigment 11

A mixture of 0.20 mol of an about 30% nickel(II) chloride solution, 0.50mol of an about 30% copper(II) chloride solution and 0.200 mol of anabout 20% erbium(III) chloride solution was added dropwise.

Example 12: Preparation of Pigment 12

A mixture of 0.20 mol of an about 30% nickel(II) chloride solution, 0.50mol of an about 30% copper(II) chloride solution, 0.100 mol of an about20% thulium(III) chloride solution and 0.100 mol of an about 20%cerium(III) chloride solution was added dropwise.

Example 13: Preparation of Pigment 13

A mixture of 0.20 mol of an about 30% nickel(II) chloride solution, 0.50mol of an about 30% copper(II) chloride solution, 0.100 mol of an about20% ytterbium(III) chloride solution and 0.100 mol of an about 20%erbium(III) chloride solution was added dropwise.

Example 14: Preparation of Pigment 14

A mixture of 0.20 mol of an about 30% nickel(II) chloride solution, 0.50mol of an about 30% copper(II) chloride solution, 0.150 mol of an about20% strontium(II) chloride solution and 0.150 mol of an about 20%magnesium(II) chloride solution was added dropwise.

Example 15: Preparation of Pigment 15

A mixture of 0.20 mol of an about 30% nickel(II) chloride solution, 0.50mol of an about 30% copper(II) chloride solution, 0.100 mol of an about20% magnesium(II) chloride solution, 0.067 mol of an about 20%terbium(III) chloride solution and 0.067 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 16: Preparation of Pigment 16

A mixture of 0.02 mol of an about 30% nickel(II) chloride solution, 0.68mol of an about 30% copper(II) chloride solution and 0.300 mol of anabout 20% calcium(II) chloride solution was added dropwise.

Example 17: Preparation of Pigment 17

A mixture of 0.02 mol of an about 30% nickel(II) chloride solution, 0.68mol of an about 30% copper(II) chloride solution, 0.150 mol of an about20% manganese(II) chloride solution and 0.150 mol of an about 20%lead(II) chloride solution was added dropwise.

Example 18: Preparation of Pigment 18

A mixture of 0.02 mol of an about 30% nickel(II) chloride solution, 0.68mol of an about 30% copper(II) chloride solution, 0.100 mol of an about20% europium(III) chloride solution and 0.150 mol of an about 20%cobalt(II) chloride solution was added dropwise.

Example 19: Preparation of Pigment 19

A mixture of 0.02 mol of an about 30% nickel(II) chloride solution, 0.68mol of an about 30% copper(II) chloride solution, 0.150 mol of an about20% cadmium(II) chloride solution and 0.150 mol of an about 20% iron(II)chloride solution was added dropwise.

Example 20: Preparation of Pigment 20

A mixture of 0.02 mol of an about 30% nickel(II) chloride solution, 0.68mol of an about 30% copper(II) chloride solution, 0.100 mol of an about20% zinc(II) chloride solution, 0.100 mol of an about 20% strontium(II)chloride solution and 0.067 mol of an about 20% aluminium(III) chloridesolution was added dropwise.

Example 21: Preparation of Pigment 21

A mixture of 0.83 mol of an about 30% nickel(II) chloride solution, 0.02mol of an about 30% copper(II) chloride solution and 0.100 mol of anabout 20% lanthanum(III) chloride solution was added dropwise.

Example 22: Preparation of Pigment 22

A mixture of 0.83 mol of an about 30% nickel(II) chloride solution, 0.02mol of an about 30% copper(II) chloride solution, 0.050 mol of an about20% cerium(III) chloride solution and 0.050 mol of an about 20%praseodymium(II) chloride solution was added dropwise.

Example 23: Preparation of Pigment 23

A mixture of 0.83 mol of an about 30% nickel(II) chloride solution, 0.02mol of an about 30% copper(II) chloride solution, 0.075 mol of an about20% magnesium(II) chloride solution and 0.050 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 24: Preparation of Pigment 24

A mixture of 0.83 mol of an about 30% nickel(II) chloride solution, 0.02mol of an about 30% copper(II) chloride solution, 0.050 mol of an about20% neodymium(III) chloride solution and 0.050 mol of an about 20%gadolinium(III) chloride solution was added dropwise.

Example 25: Preparation of Pigment 25

A mixture of 0.83 mol of an about 30% nickel(II) chloride solution, 0.02mol of an about 30% copper(II) chloride solution, 0.033 mol of an about20% samarium(III) chloride solution, 0.050 mol of an about 20% lead(II)chloride solution and 0.050 mol of an about 20% calcium(II) chloridesolution was added dropwise.

Example 26: Preparation of Pigment 26

A mixture of 0.45 mol of an about 30% nickel(II) chloride solution, 0.40mol of an about 30% copper(II) chloride solution and 0.100 mol of anabout 20% europium(III) chloride solution was added dropwise.

Example 27: Preparation of Pigment 27

A mixture of 0.45 mol of an about 30% nickel(II) chloride solution, 0.40mol of an about 30% copper(II) chloride solution, 0.050 mol of an about20% samarium(III) chloride solution and 0.050 mol of an about 20%gadolinium(III) chloride solution was added dropwise.

Example 28: Preparation of Pigment 28

A mixture of 0.45 mol of an about 30% nickel(II) chloride solution, 0.40mol of an about 30% cooper(II) chloride solution, 0.050 mol of an about20% terbium(III) chloride solution and 0.050 mol of an about 20%holmium(III) chloride solution was added dropwise.

Example 29: Preparation of Pigment 29

A mixture of 0.45 mol of an about 30% nickel(II) chloride solution, 0.40mol of an about 30% copper(II) chloride solution, 0.050 mol of an about20% dysprosium(III) chloride solution and 0.050 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 30: Preparation of Pigment 30

A mixture of 0.45 mol of an about 30% nickel(II) chloride solution, 0.40mol of an about 30% copper(II) chloride solution, 0.033 mol of an about20% holmium(III) chloride solution, 0.033 mol of an about 20%thulium(III) chloride solution and 0.050 mol of an about 20%manganese(II) chloride solution was added dropwise.

Example 31: Preparation of Pigment 31

A mixture of 0.20 mol of an about 30% nickel(II) chloride solution, 0.65mol of an about 30% copper(II) chloride solution and 0.100 mol of anabout 20% erbium(III) chloride solution was added dropwise.

Example 32: Preparation of Pigment 32

A mixture of 0.20 mol of an about 30% nickel(II) chloride solution, 0.65mol of an about 30% copper(II) chloride solution, 0.050 mol of an about20% thulium(III) chloride solution and 0.050 mol of an about 20%cerium(III) chloride solution was added dropwise.

Example 33: Preparation of Pigment 33

A mixture of 0.20 mol of an about 30% nickel(II) chloride solution, 0.65mol of an about 30% copper(II) chloride solution, 0.050 mol of an about20% ytterbium(III) chloride solution and 0.050 mol of an about 20%erbium(II) chloride solution was added dropwise.

Example 34: Preparation of Pigment 34

A mixture of 0.20 mol of an about 30% nickel(II) chloride solution, 0.65mol of an about 30% copper(II) chloride solution, 0.075 mol of an about20% strontium(II) chloride solution and 0.075 mol of an about 20%magnesium(II) chloride solution was added dropwise.

Example 35: Preparation of Pigment 35

A mixture of 0.20 mol of an about 30% nickel(II) chloride solution, 0.65mol of an about 30% copper(II) chloride solution, 0.075 mol of an about20% magnesium(II) chloride solution, 0.033 mol of an about 20%terbium(III) chloride solution and 0.033 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 36: Preparation of Pigment 36

A mixture of 0.02 mol of an about 30% nickel(II) chloride solution, 0.83mol of an about 30% copper(II) chloride solution and 0.150 mol of anabout 20% calcium(II) chloride solution was added dropwise.

Example 37: Preparation of Pigment 37

A mixture of 0.02 mol of an about 30% nickel(II) chloride solution, 0.83mol of an about 30% copper(II) chloride solution, 0.075 mol of an about20% manganese(ii) chloride solution and 0.075 mol of an about 20%lead(II) chloride solution was added dropwise.

Example 38: Preparation of Pigment 38

A mixture of 0.02 mol of an about 30% nickel(II) chloride solution, 0.83mol of an about 30% copper(II) chloride solution, 0.050 mol of an about20% europium(III) chloride solution and 0.075 mol of an about 20%cobalt(II) chloride solution was added dropwise.

Example 39: Preparation of Pigment 39

A mixture of 0.02 mol of an about 30% nickel(II) chloride solution, 0.83mol of an about 30% copper(II) chloride solution, 0.075 mol of an about20% cadmium(II) chloride solution and 0.075 mol of an about 20% iron(II)chloride solution was added dropwise.

Example 40: Preparation of Pigment 40

A mixture of 0.02 mol of an about 30% nickel(II) chloride solution, 0.83mol of an about 30% copper(II) chloride solution, 0.050 mol of an about20% zinc(II) chloride solution, 0.050 mol of an about 20% strontium(II)chloride solution and 0.033 mol of an about 20% aluminium(III) chloridesolution was added dropwise.

Example 41: Preparation of Pigment 41

A mixture of 0.90 mol of an about 30% nickel(II) chloride solution, 0.03mol of an about 30% copper(II) chloride solution and 0.047 mol of anabout 20% lanthanum(III) chloride solution was added dropwise.

Example 42: Preparation of Pigment 42

A mixture of 0.90 mol of an about 30% nickel(II) chloride solution, 0.03mol of an about 30% copper(II) chloride solution, 0.023 mol of an about20% cerium(III) chloride solution and 0.023 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 43: Preparation of Pigment 43

A mixture of 0.90 mol of an about 30% nickel(II) chloride solution, 0.03mol of an about 30% copper(II) chloride solution, 0.035 mol of an about20% magnesium(II) chloride solution and 0.023 mol of an about 20%praseodymium(III) chloride solution was added drop ice.

Example 44: Preparation of Pigment 44

A mixture of 0.90 mol of an about 30% nickel(II) chloride solution, 0.03mol of an about 30% copper(II) chloride solution, 0.023 mol of an about20% neodymium(III) chloride solution and 0.023 mol of an about 20%gadolinium(III) chloride solution was added dropwise.

Example 45: Preparation of Pigment 45

A mixture of 0.90 mol of an about 30% nickel(II) chloride solution, 0.03mol of an about 30% copper(II) chloride solution, 0.013 mol of an about20% samarium(III) chloride solution, 0.020 mol of an about 20% lead(II)chloride solution and 0.030 mol of an about 20% calcium(II) chloridesolution was added dropwise.

Example 46: Preparation of Pigment 46

A mixture of 0.50 mol of an about 30% nickel(II) chloride solution, 0.43mol of an about 30% copper(II) chloride solution and 0.047 mol of anabout 20% europium(III) chloride solution was added dropwise.

Example 47: Preparation of Pigment 47

A mixture of 0.50 mol of an about 30% nickel(II) chloride solution, 0.43mol of an about 30% copper(II) chloride solution, 0.023 mol of an about20% samarium(III) chloride solution and 0.023 mol of an about 20%gadolinium(III) chloride solution was added dropwise.

Example 48: Preparation of Pigment 48

A mixture of 0.50 mol of an about 30% nickel(II) chloride solution, 0.43mol of an about 30% copper(II) chloride solution, 0.023 mol of an about20% terbium(III) chloride solution and 0.023 mol of an about 20%holmium(III) chloride solution was added dropwise.

Example 49: Preparation of Pigment 49

A mixture of 0.50 mol of an about 30% nickel(II) chloride solution, 0.43mol of an about 30% copper(II) chloride solution, 0.023 mol of an about20% dysprosium(III) chloride solution and 0.023 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 50: Preparation of Pigment 50

A mixture of 0.50 mol of an about 30% nickel(II) chloride solution, 0.43mol of an about 30% copper(II) chloride solution, 0.013 mol of an about20% holmium(III) chloride solution, 0.013 mol of an about 20%thulium(III) chloride solution and 0.030 mol of an about 20%manganese(It) chloride solution was added dropwise.

Example 51: Preparation of Pigment 51

A mixture of 0.23 mol of an about 30% nickel(II) chloride solution, 0.70mol of an about 30% copper(II) chloride solution and 0.047 mol of anabout 20% erbium(III) chloride solution was added dropwise.

Example 52: Preparation of Pigment 52

A mixture of 0.23 mol of an about 30% nickel(II) chloride solution, 0.70mol of an about 30% copper(II) chloride solution, 0.023 mol of an about20% thulium(III) chloride solution and 0.023 mol of an about 20%cerium(III) chloride solution was added dropwise.

Example 53: Preparation of Pigment 53

A mixture of 0.23 mol of an about 30% nickel(II) chloride solution, 0.70mol of an about 30% copper(II) chloride solution, 0.023 mol of an about20% ytterbium(III) chloride solution and 0.023 mol of an about 20%erbium(III) chloride solution was added dropwise.

Example 54: Preparation of Pigment 54

A mixture of 0.23 mol of an about 30% nickel(II) chloride solution, 0.70mol of an about 30% copper(II) chloride solution, 0.035 mol of an about20% strontium(II) chloride solution and 0.035 mol of an about 20%magnesium(II) chloride solution was added dropwise.

Example 55: Preparation of Pigment 55

A mixture of 0.23 mol of an about 30% nickel(II) chloride solution, 0.70mol of an about 30% copper(II) chloride solution, 0.020 mol of an about20% magnesium(II) chloride solution, 0.013 mol of an about 20%terbium(III) chloride solution and 0.020 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 56: Preparation of Pigment 56

A mixture of 0.03 mol of an about 30% nickel(II) chloride solution, 0.90mol of an about 30% cooper(II) chloride solution and 0.070 mol of anabout 20% calcium(II) chloride solution was added dropwise.

Example 57: Preparation of Pigment 57

A mixture of 0.03 mol of an about 30% nickel(II) chloride solution, 0.90mol of an about 30% copper(II) chloride solution, 0.035 mol of an about20% manganese(II) chloride solution and 0.035 mol of an about 20%lead(II) chloride solution was added dropwise.

Example 58: Preparation of Pigment 58

A mixture of 0.03 mol of an about 30% nickel(H) chloride solution, 0.90mol of an about 30% copper(II) chloride solution, 0.023 mol of an about20% europium(III) chloride solution and 0.035 mol of an about 20%cobalt(II) chloride solution was added dropwise.

Example 59: Preparation of Pigment 59

A mixture of 0.03 mol of an about 30% nickel(II) chloride solution, 0.90mol of en about 30% copper(II) chloride solution, 0.035 mol of an about20% cadmium(II) chloride solution and 0.035 mol of an about 20% iron(II)chloride solution was added dropwise.

Example 60: Preparation of Pigment 60

A mixture of 0.03 mol of an about 30% nickel(II) chloride solution, 0.90mol of an about 30% copper(II) chloride solution, 0.020 mol of an about20% zinc(II) chloride solution, 0.020 mol of an about 20% strontium(II)chloride solution and 0.020 mol of an about 20% aluminium(III) chloridesolution was added dropwise.

Example 61: Preparation of Pigment 61

A mixture of 0.92 mol of an about 30% nickel(II) chloride solution, 0.05mol of an about 30% copper(II) chloride solution and 0.020 mol of anabout 20% lanthanum(III) chloride solution was added dropwise.

Example 62: Preparation of Pigment 62

A mixture of 0.92 mol of an about 30% nickel(II) chloride solution, 0.05mol of an about 30% copper(II) chloride solution, 0.010 mol of an about20% cerium(III) chloride solution and 0.010 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 63: Preparation of Pigment 63

A mixture of 0.92 mol of an about 30% nickel(II) chloride solution, 0.05mol of an about 30% copper(II) chloride solution, 0.015 mol of an about20% magnesium(II) chloride solution and 0.010 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 64: Preparation of Pigment 64

A mixture of 0.92 mol of an about 30% nickel(II) chloride solution, 0.05mol of an about 30% copper(II) chloride solution, 0.010 mol of an about20% neodymium(III) chloride solution and 0.010 mol of an about 20%gadolinium(III) chloride solution was added dropwise.

Example 65: Preparation of Pigment 66

A mixture of 0.92 mol of an about 30% nickel(II) chloride solution, 0.05mol of an about 30% copper(II) chloride solution, 0.0067 mol of an about20% samarium(III) chloride solution, 0.010 mol of an about 20% lead(II)chloride solution and 0.010 mol of an about 20% calcium(II) chloridesolution was added dropwise.

Example 66: Preparation of Pigment 66

A mixture of 0.50 mol of an about 30% nickel(II) chloride solution, 0.47mol of an about 30% copper(II) chloride solution and 0.020 mol of anabout 20% europium(III) chloride solution was added dropwise.

Example 67: Preparation of Pigment 67

A mixture of 0.50 mol of an about 30% nickel(II) chloride solution, 0.47mol of an about 30% copper(II) chloride solution, 0.010 mol of an about20% samarium(III) chloride solution and 0.010 mol of an about 20%gadolinium(III) chloride solution was added dropwise.

Example 68: Preparation of Pigment 68

A mixture of 0.50 mol of an about 30% nickel(II) chloride so/titian,0.47 mol of an about 30% copper(II) chloride solution, 0.010 mol of anabout 20% terbium(III) chloride solution and 0.010 mol of an about 20%holmium(III) chloride solution was added dropwise.

Example 69: Preparation of Pigment 69

A mixture of 0.50 mol of an about 30% nickel(II) chloride solution, 047mol of an about 30% copper(II) chloride solution, 0.010 mol of an about20% dysprosium(III) chloride solution and 0.010 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 70: Preparation of Pigment 70

A mixture of 0.50 mol of an about 30% nickel(II) chloride solution, 0.47mol of an about 30% copper(II) chloride solution, 0.0067 mol of an about20% holmium(III) chloride solution, 0.0067 mol of an about 20%thulium(III) chloride solution and 0.010 mol of an about 20%manganese(II) chloride solution was added dropwise.

Example 71: Preparation of Pigment 71

A mixture of 025 mol of an about 30% nickel(II) chloride solution, 0.72mol of an about 30% copper(II) chloride solution and 0.020 mol of anabout 20% erbium(III) chloride solution was added dropwise.

Example 72: Preparation of Pigment 72

A mixture of 0.25 mol of an about 30% nickel(II) chloride solution, 0.72mol of an about 30% copper(II) chloride solution, 0.010 mol of an about20% thulium(III) chloride solution and 0.010 mol of an about 20%cerium(III) chloride solution was added dropwise.

Example 73: Preparation of Pigment 73

A mixture of 0.25 mol of an about 30% nickel(II) chloride solution, 0.72mol of an about 30% copper(II) chloride solution, 0.010 mol of an about20% ytterbium(III) chloride solution and 0.010 mol of an about 20%erbium(III) chloride solution was added dropwise.

Example 74: Preparation of Pigment 74

A mixture of 0.25 mol of an about 30% nickel(II) chloride solution, 0.72mol of an about 30% copper(II) chloride solution, 0.015 mol of an about20% strontium(II) chloride solution and 0.015 mol of an about 20%magnesium(II) chloride solution was added dropwise.

Example 75: Preparation of Pigment 75

A mixture of 0.25 mol of an about 30% nickel(II) chloride solution, 0.72mol of an about 30% copper(10 chloride solution, 0.010 mol of an about20% magnesium(II) chloride solution, 0.0067 mol of an about 20%terbium(III) chloride solution end 0.0067 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 76: Preparation of Pigment 76

A mixture of 0.05 mol of an about 30% nickel(II) chloride solution, 0.92mol of an about 30% copper(II) chloride solution and 0.030 mol of anabout 20% calcium(II) chloride solution was added dropwise.

Example 77: Preparation of Pigment 77

A mixture of 0.05 mol of an about 30% nickel(II) chloride solution, 0.92mol of an about 30% copper(II) chloride solution, 0.015 mol of an about20% manganese(II) chloride solution and 0.015 mol of an about 20%lead(II) chloride solution was added dropwise.

Example 78: Preparation of Pigment 78

A mixture of 0.05 mol of an about 30% nickel(II) chloride solution, 0.92mol of an about 30% cooper(II) chloride solution, 0.010 mol of an about20% europium(III) chloride solution and 0.015 mol of an about 20%cobalt(II) chloride solution was added dropwise.

Example 79: Preparation of Pigment 79

A mixture of 0.05 mol of an about 30% nickel(II) chloride solution, 0.92mol of an about 30% copper(II) chloride solution, 0.015 mol of an about20% cadmium(II) chloride solution and 0.015 mol of an about 20% iron(II)chloride solution was added dropwise.

Example 80: Preparation of Pigment 80

A mixture of 0.05 mol of an about 30% nickel(II) chloride solution, 0.92mol of an about 30% copper(II) chloride solution, 0.010 mol of an about20% zinc(II) chloride solution, 0.010 mol of an about 20% strontium(II)chloride solution and 0.0067 mol of an about 20% aluminium(III) chloridesolution was added dropwise.

Example 81: Preparation of Pigment 81

A mixture of 0.96 mol of an about 30% nickel(II) chloride solution,0.035 mol of an about 30% copper(II) chloride solution and 0.0033 mol ofan about 20% lanthanum(III) chloride solution was added dropwise.

Example 82: Preparation of Pigment 82

A mixture of 0.96 mol of an about 30% nickel(II) chloride solution,0.035 mol of an about 30% copper(II) chloride solution, 0.0017 mol of anabout 20% cerium(III) chloride solution and 0.0017 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 83: Preparation of Pigment 83

A mixture of 0.96 mol of an about 30% nickel(II) chloride solution,0.035 mol of an about 30% copper(II) chloride solution, 0.0025 mol of anabout 20% magnesium(II) chloride solution and 0.0017 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 84: Preparation of Pigment 84

A mixture of 0.96 mol of an about 30% nickel(II) chloride solution,0.035 mol of an about 30% copper(II) chloride solution, 0.0017 mol of anabout 20% neodymium(III) chloride solution and 0.0017 mol of an about20% gadolinium(III) chloride solution was added dropwise.

Example 85: Preparation of Pigment 85

A mixture of 0.96 mol of an about 30% nickel(II) chloride solution,0.035 mol of an about 30% copper(II) chloride solution, 0.0013 mol of anabout 20% samarium(III) chloride solution, 0.0020 mol of an about 20%lead(II) chloride solution and 0.0010 mol of an about 20% calcium(II)chloride solution was added dropwise.

Example 86: Preparation of Pigment 86

A mixture of 0.50 mol of an about 30% nickel(II) chloride solution,0.495 mol of an about 30% copper(II) chloride solution and 0.0033 mol ofan about 20% europium(III) chloride solution was added dropwise.

Example 87: Preparation of Pigment 87

A mixture of 0.50 mol of an about 30% nickel(II) chloride solution,0.495 mol of an about 30% copper(II) chloride solution, 0.0017 mol of anabout 20% samarium(III) chloride solution and 0.0017 mol of an about 20%gadolinium(III) chloride solution was added dropwise.

Example 88: Preparation of Pigment 88

A mixture of 0.50 mol of an about 30% nickel(II) chloride solution,0.495 mol of an about 30% copper(II) chloride solution, 0.0017 mol of anabout 20% terbium(III) chloride solution and 0.0017 mol of an about 20%holmium(III) chloride solution was added dropwise.

Example 89: Preparation of Pigment 89

A mixture of 0.50 mol of an about 30% nickel(II) chloride solution,0.495 mol of an about 30% copper(II) chloride solution, 0.0017 mol of anabout 20% dysprosium(III) chloride solution and 0.0017 mol of an about20% praseodymium(III) chloride solution was added dropwise.

Example 90: Preparation of Pigment 90

A mixture of 0.50 mol of an about 30% nickel(II) chloride solution,0.495 mol of an about 30% copper(II) chloride solution, 0.0013 mol of anabout 20% holmium(III) chloride solution, 0.0013 mol of an about 20%thulium(III) chloride solution and 0.0010 mol of an about 20%manganese(II) chloride solution was added dropwise.

Example 91: Preparation of Pigment 91

A mixture of 0.25 mol of an about 30% nickel(II) chloride solution,0.745 mol of an about 30% copper(II) chloride solution and 0.033 mol ofan about 20% erbium(III) chloride solution was added dropwise.

Example 92: Preparation of Pigment 92

A mixture of 0.25 mol of an about 30% nickel(II) chloride solution,0.745 mol of an about 30% copper(II) chloride solution, 0.0017 mol of anabout 20% thulium(III) chloride solution and 0.0017 mol of an about 20%cerium(III) chloride solution was added dropwise.

Example 93: Preparation of Pigment 93

A mixture of 0.25 mol of an about 30% nickel(II) chloride solution,0.745 mol of an about 30% copper(II) chloride solution, 0.0017 mol of anabout 20% ytterbium(III) chloride solution and 0.0017 mol of an about20% erbium(III) chloride solution was added dropwise.

Example 94: Preparation of Pigment 94

A mixture of 0.25 mol of an about 30% nickel(II) chloride solution,0.745 mol of an about 30% copper(II) chloride solution, 0.0025 mol of anabout 20% strontium(II) chloride solution and 0.0025 mol of an about 20%magnesium(II) chloride solution was added dropwise.

Example 95: Preparation of Pigment 95

A mixture of 0.25 mol of an about 30% nickel(II) chloride solution,0.745 mol of an about 30% copper(II) chloride solution, 0.0020 mol of anabout 20% magnesium(II) chloride solution, 0.0013 mol of an about 20%terbium(III) chloride solution and 0.00067 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 96: Preparation of Pigment 96

A mixture of 0.035 mol of an about 30% nickel(II) chloride solution,0.96 mol of an about 30% copper(II) chloride solution and 0.005 mol ofan about 20% calcium(II) chloride solution was added dropwise.

Example 97: Preparation of Pigment 97

A mixture of 0.035 mol of an about 30% nickel(II) chloride solution,0.96 mol of an about 30% copper(II) chloride solution, 0.0025 mol of anabout 20% manganese(H) chloride solution and 0.0025 mol of an about 20%lead(II) chloride solution was added dropwise.

Example 98: Preparation of Pigment 98

A mixture of 0.035 mol of an about 30% nickel(II) chloride solution,0.95 mol of an about 30% copper(II) chloride solution, 0.0017 mol of anabout 20% europium(III) chloride solution and 0.0025 mol of an about 20%cobalt(II) chloride solution was added dropwise.

Example 99: Preparation of Pigment 99

A mixture of 0.035 mol of an about 30% nickel(II) chloride solution,0.96 mol of an about 30% copper(II) chloride solution, 0.0025 mol of anabout 20% cadmium(II) chloride solution and 0.0025 mol of an about 20%iron(II) chloride solution was added dropwise.

Example 100: Preparation of Pigment 100

A mixture of 0.035 mol of an about 30% nickel(II) chloride solution,0.96 mol of an about 30% copper(II) chloride solution, 0.0020 mol of anabout 20% zinc(II) chloride solution, 0.0020 mol of an about 20%strontium(II) chloride solution and 0.00067 mol of an about 20%aluminium(III) chloride solution was added dropwise.

Example 101: Preparation of Pigment 101 (Noninventive)

A mixture of 0.63 mol of an about 30% nickel(II) chloride solution, 0.02mol of an about 30% copper(II) chloride solution and 0.223 mol of anabout 20% lanthanum(III) chloride solution was added dropwise.

Example 102: Preparation of Pigment 102 (Noninventive)

A mixture of 0.63 mol of an about 30% nickel(II) chloride solution, 0.02mol of an about 30% copper(II) chloride solution, 0.117 mol of an about20% cerium(III) chloride solution and 0.117 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 103: Preparation of Pigment 163 (Noninventive)

A mixture of 0.63 mol of an about 30% nickel(II) chloride solution, 0.02mol of an about 30% copper(II) chloride solution, 0.175 mol of an about20% magnesium(II) chloride solution and 0.117 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 104: Preparation of Pigment 108 (Noninventive)

A mixture of 0.63 mol of an about 30% nickel(II) chloride solution, 0.02mol of an about 30% copper(II) chloride solution, 0.117 mol of an about20% neodymium(III) chloride solution end 0.117 mol of an about 20%gadolinium(III) chloride solution was added dropwise.

Example 105: Preparation of Pigment 105 (Noninventive)

A mixture of 0.63 mol of an about 30% nickel(II) chloride solution, 0.02mol of an about 30% copper(II) chloride solution, 0.067 mol of an about20% samarium(III) chloride solution, 0.10 mol of an about 20% lead(II)chloride solution and 0.10 mol of an about 20% calcium(II) chloridesolution was added dropwise.

Example 106: Preparation of Pigment 106 (Noninventive)

A mixture of 0.35 mol of an about 30% nickel(II) chloride solution, 0.30mol of an about 30% copper(II) chloride solution and 0.233 mol of anabout 20% europium(III) chloride solution was added dropwise.

Example 107: Preparation of Pigment 107 (Noninventive)

A mixture of 0.35 mol of an about 30% nickel(II) chloride solution, 0.30mol of an about 30% copper(II) chloride solution, 0.117 mol of an about20% samarium(III) chloride solution and 0.117 mol of an about 20%gadolinium(III) chloride solution was added dropwise.

Example 108: Preparation of Pigment 108 (Noninventive)

A mixture of 0.35 mol of an about 30% nickel(II) chloride solution, 0.30mol of an about 30% copper(II) chloride solution, 0.117 mol of an about20% terbium(III) chloride solution and 0.117 mol of an about 20%holmium(III) chloride solution was added dropwise.

Example 109: Preparation of Pigment 109 (Noninventive)

A mixture of 0.35 mol of an about 30% nickel(II) chloride solution, 0.30mol of an about 30% copper(II) chloride solution, 0.117 mol of an about20% dysprosium(III) chloride solution and 0.117 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 110: Preparation of Pigment 110 (Noninventive)

A mixture of 0.35 mol of an about 30% nickel(II) chloride solution, 0.30mol of an about 30% copper(II) chloride solution, 0.067 mol of an about20% holmium(III) chloride solution, 0.067 mol of an about 20%thulium(III) chloride solution and 0.15 mol of an about 20%manganese(II) chloride solution was added dropwise.

Example 111: Preparation of Pigment 111 (Noninventive)

A mixture of 0.15 mol of an about 30% nickel(II) chloride solution, 0.50mol of an about 30% copper(II) chloride solution and 0.233 mol of anabout 20% erbium(III) chloride solution was added dropwise.

Example 112: Preparation of Pigment 112 (Noninventive)

A mixture of 0.15 mol of an about 30% nickel(II) chloride solution, 0.50mol of an about 30% copper(II) chloride solution, 0.117 mol of an about20% thulium(III) chloride solution and 0.117 mol of an about 20%cerium(III) chloride solution was added dropwise.

Example 113: Preparation of Pigment 113 (Noninventive)

A mixture of 0.15 mol of an about 30% nickel(II) chloride solution, 0.50mol of an about 30% copper(II) chloride solution, 0.117 mol of an about20% ytterbium(III) chloride solution and 0.117 mol of an about 20%erbium(III) chloride solution was added dropwise.

Example 114: Preparation of Pigment 114 (Noninventive)

A mixture of 0.15 mol of an about 30% nickel(II) chloride solution, 0.50mol of an about 30% copper(II) chloride solution, 0.175 mol of an about20% strontium(II) chloride solution and 0.175 mol of an about 20%magnesium(II) chloride solution was added dropwise.

Example 115: Preparation of Pigment 115 (Noninventive)

A mixture of 0.15 mol of an about 30% nickel(II) chloride solution, 0.50mol of an about 30% cooper(II) chloride solution, 0.10 mol of an about20% magnesium(II) chloride solution, 0.067 mol of an about 20%terbium(III) chloride solution and 0.067 mol of an about 20%praseodymium(III) chloride solution was added dropwise.

Example 116: Preparation of Pigment 116 (Noninventive)

A mixture of 0.02 mol of an about 30% nickel(II) chloride solution, 0.63mol of an about 30% copper(II) chloride solution and 0.35 mol of anabout 20% calcium(II) chloride solution was added dropwise.

Example 117: Preparation of Pigment 117 (Noninventive)

A mixture of 0.02 mol of an about 30% nickel(II) chloride solution, 0.63mol of an about 30% copper(II) chloride solution, 0.175 mol of an about20% manganese(II) chloride solution and 0.175 mol of an about 20%lead(II) chloride solution was added dropwise.

Example 118: Preparation of Pigment 118 (Noninventive)

A mixture of (102 mol of an about 30% nickel (II) chloride solution,0.83 mol of an about 30% copper chloride solution, 0.117 mol of an about20% europium(III) chloride solution and 0.175 mol of an about 20%cobalt(II) chloride solution was added dropwise.

Example 119: Preparation of Pigment 119 (Noninventive)

A mixture of 0.02 mol of an about 30% nickel(II) chloride solution, 0.63mol of an about 30% copper(I) chloride solution, 0.175 mol of an about20% cadmium(II) chloride solution and 0.175 mol of an about 20% iron(II)chloride solution was added dropwise.

Example 120: Preparation of Pigment 120 (Noninventive)

A mixture of 0.02 mol of an about 30% nickel(II) chloride solution, 0.83mol of an about 30% copper(II) chloride solution, 0.10 mol of an about20% zinc(II) chloride solution, 0.10 mol of an about 20% strontium(II)chloride solution and 0.067 mol of an about 20% aluminium(III) chloridesolution was added dropwise.

Example 121: Preparation of Pigment 121 (Noninventive)

A mixture of 0.9714 mol of an about 30% nickel(II) chloride solution and0.0286 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 122: Preparation of Pigment 122 (Noninventive)

A mixture of 0.50 mol of an about 30% nickel(II) chloride solution and0.50 mol of an about 30% cooper(II) chloride solution was addeddropwise.

Example 123: Preparation of Pigment 123 (Noninventive)

A mixture of 0.2857 mol of an about 30% nickel(II) chloride solution and0.7143 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 124: Preparation of Pigment 124 (Noninventive)

A mixture of 0.0286 mol of an about 30% nickel(II) chloride solution and0.9714 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 125: Preparation of Pigment 125 (Noninventive)

A mixture of 0.9765 mol of an about 30% nickel(II) chloride solution and0.235 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 126: Preparation of Pigment 126 (Noninventive)

A mixture of 0.5294 mol of an about 30% nickel(II) chloride solution and0.4706 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 127: Preparation of Pigment 127 (Noninventive)

A mixture of 0.2353 mol of an about 30% nickel(II) chloride solution and0.647 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 128: Preparation of Pigment 128 (Noninventive)

A mixture of 0.9765 mol of an about 30% nickel(II) chloride solution and00235 mol of an about 30% cooper(II) chloride solution was addeddropwise.

Example 129: Preparation of Pigment 129 (Noninventive)

A mixture of 0.9677 mol of an about 30% nickel(II) chloride solution and0.0323 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 130: Preparation of Pigment 130 (Noninventive)

A mixture of 0.5376 mol of an about 30% nickel(II) chloride solution and0.4624 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 131: Preparation of Pigment 131 (Noninventive)

A mixture of 0.2473 mol of an about 30% nickel(II) chloride solution and0.7527 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 132: Preparation of Pigment 132 (Noninventive)

A mixture of 0.0323 mol of an about 30% nickel(II) chloride solution and0.9677 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 133: Preparation of Pigment 133 (Noninventive)

A mixture of 0.9485 mol of an about 30% nickel(II) chloride solution and0.0515 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 134: Preparation of Pigment 134 (Noninventive)

A mixture of 0.5155 mol of en about 30% nickel(II) chloride solution and0.4845 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 135: Preparation of Pigment 135 (Noninventive)

A mixture of 0.2577 mol of an about 30% nickel(II) chloride solution and0.7423 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 136: Preparation of Pigment 136 (Noninventive)

A mixture of 0.0515 mol of an about 30% nickel(II) chloride solution and0.9485 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 137: Preparation of Pigment 137 (Noninventive)

A mixture of 0.9648 mol of an about 30% nickel(II) chloride solution and0.0352 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 136: Preparation of Pigment 138 (Noninventive)

A mixture of 0.5025 mol of an about 30% nickel(II) chloride solution and0.4975 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 139: Preparation of Pigment 139 (Noninventive)

A mixture of 0.2513 mol of an about 30% nickel(II) chloride solution and0.7487 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 140: Preparation of Pigment 140 (Noninventive)

A mixture of 0.0352 mol of an about 30% nickel(II) chloride solution and0.9648 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 141: Preparation of Pigment 141 (Noninventive)

A mixture of 0.9692 mol of an about 30% nickel(II) chloride solution and0.0308 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 142: Preparation of Pigment 142 (Noninventive)

A mixture of 0.5385 mol of an about 30% nickel(II) chloride solution and0.4615 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 143: Preparation of Pigment 143 (Noninventive)

A mixture of 0.2308 mol of an about 30% nickel(II) chloride solution and0.7692 mol of an about 30% copper(II) chloride solution was addeddropwise.

Example 144: Preparation of Pigment 144 (Noninventive)

A mixture of 0.0308 mol of an about 30% nickel(II) chloride solution and0.9692 mol of an about 30% copper(II) chloride solution was addeddropwise.

Determination of Colour Strength in PVC

The pigments 1 to 144 prepared according to Examples 1 to 144 were eachsubjected to a determination of colour strength by the method whichfollows. The results are listed in Table 1.

The test medium produced was a flexible PVC compound, by homogenizing67.5% Vestolit® E7004 (Vestolit GmbH), 29.0% Hexamoll® Dinch (BASF),2.25% Baerostab UBZ 770 (Baerlocher GmbH) and 1.25% Isocolor whitepigment paste (ISL-Chemie) with a laboratory dissolver.

A laboratory roll mill was used to add 100 g of the PVC compound at 150°C. to two rollers of diameter 150 mm that rotate at 20 min⁻¹ and 18min⁻¹. Together with 0.10 g of pigment, the allied sheet that formed wasguided through a roger gap of 0.10 mm eight times. Then thehomogeneously coloured milled sheet was removed with a roger gap of 0.8mm and laid out flat over a metal surface. The cooled milled sheet wasthen passed through a roller gap of 0.2 mm between two unheated rollersof diameter 110 mm that rotate at 26 min⁻¹ and 24 min⁻¹ eight times. Tosmooth the surface, this milled sheet was applied to the rollers at 150°C. once again, removed at 0.8 mm and left to cool on a smooth surface.Specimens of this sheet served to determine the relative colourstrength.

The relative colour strength was calculated after measuring thereflectance of the specimens against a white background by means of aspectrophotometer with d/8 measurement geometry under D65 illuminantwith a 10° observer according to DIN 55986 using the sum total of theK/S values over the visible spectrum (400 nm-700 nm),

TABLE 1 Molar Ni/Cu Colour Sample Status ratio strength % Pigment 1:inventive  1.00:0.0294 114 Pigment 2: inventive  1.00:0.0294 115 Pigment3: inventive  1.00:0.0294 114 Pigment 4: inventive  1.00:0.0294 113Pigment 5: inventive  1.00:0.0294 115 Pigment 6: inventive 1.00:1.00 114 Pigment 7: inventive 1.00:1.00  113 Pigment 8: inventive 1.00:1.00 113 Pigment 9: inventive 1.00:1.00  115 Pigment 10: inventive 1.00:1.00 114 Pigment 11: inventive 1.00:2.50  113 Pigment 12: inventive1.00:2.50  115 Pigment 13: inventive 1.00:2.50  112 Pigment 14:inventive 1.00:2.50  111 Pigment 15: inventive 1.00:2.50  115 Pigment16: inventive 1.00:34.00 116 Pigment 17: inventive 1.00:34.00 115Pigment 18: inventive 1.00:34.00 115 Pigment 19: inventive 1.00:34.00112 Pigment 20: inventive 1.00:34.00 115 Pigment 21: inventive 1.00:0.0241 126 Pigment 22: inventive  1.00:0.0241 127 Pigment 23:inventive  1.00:0.0241 128 Pigment 24: inventive  1.00:0.0241 125Pigment 25: inventive  1.00:0.0241 125 Pigment 26: inventive 1.00:0.8889 124 Pigment 27: inventive  1.00:0.8889 122 Pigment 28:inventive  1.00:0.8889 120 Pigment 29: inventive  1.00:0.8889 122Pigment 30: inventive  1.00:0.8889 125 Pigment 31: inventive 1.00:3.25 121 Pigment 32: inventive 1.00:3.25  124 Pigment 33: inventive1.00:3.25  120 Pigment 34: inventive 1.00:3.25  122 Pigment 35:inventive 1.00:3.25  123 Pigment 36: inventive 1.00:41.50 122 Pigment37: inventive 1.00:41.50 121 Pigment 38: inventive 1.00:41.50 122Pigment 39: inventive 1.00:41.50 123 Pigment 40: inventive 1.00:41.50124 Pigment 41: inventive  1.00:0.0333 115 Pigment 42: inventive 1.00:0.0333 115 Pigment 43: inventive  1.00:0.0333 114 Pigment 44:inventive  1.00:0.0333 111 Pigment 45: inventive  1.00:0.0333 115Pigment 46: inventive 1.00:0.860 116 Pigment 47: inventive 1.00:0.860117 Pigment 48: inventive 1.00:0.860 115 Pigment 49: inventive1.00:0.860 113 Pigment 50: inventive 1.00:0.860 114 Pigment 51:inventive  1.00:3.0435 116 Pigment 52: inventive  1.00:3.0435 112Pigment 53: inventive  1.00:3.0435 111 Pigment 54: inventive 1.00:3.0435 113 Pigment 55: inventive  1.00:3.0435 112 Pigment 56:inventive 1.00:30.00 114 Pigment 57: inventive 1.00:30.00 115 Pigment58: inventive 1.00:30.00 112 Pigment 59: inventive 1.00:30.00 111Pigment 60: inventive 1.00:30.00 113 Pigment 61: inventive  1.00:0.0543109 Pigment 62: inventive  1.00:0.0543 108 Pigment 63: inventive 1.00:0.0543 107 Pigment 64: inventive  1.00:0.0543 108 Pigment 65:inventive  1.00:0.0543 109 Pigment 66: inventive 1.00:0.940 108 Pigment67: inventive 1.00:0.940 107 Pigment 68: inventive 1.00:0.940 109Pigment 69: inventive 1.00:0.940 108 Pigment 70: inventive 1.00:0.940110 Pigment 71: inventive 1.00:2.880 109 Pigment 72: inventive1.00:2.880 108 Pigment 73: inventive 1.00:2.880 107 Pigment 74:inventive 1.00:2.880 109 Pigment 75: inventive 1.00:2.880 107 Pigment76: inventive 1.00:18.40 108 Pigment 77: inventive 1.00:18.40 107Pigment 78: inventive 1.00:18.40 108 Pigment 79: inventive 1.00:18.40109 Pigment 80: inventive 1.00:18.40 107 Pigment 81: inventive 1.00:0.0365 106 Pigment 82: inventive  1.00:0.0365 105 Pigment 83:inventive  1.00:0.0365 104 Pigment 84: inventive  1.00:0.0365 103Pigment 85: inventive  1.00:0.0365 104 Pigment 86: inventive 1.00:0.990105 Pigment 87: inventive 1.00:0.990 105 Pigment 88: inventive1.00:0.990 105 Pigment 89: inventive 1.00:0.990 104 Pigment 90:inventive 1.00:0.990 102 Pigment 91: inventive 1.00:2.980 103 Pigment92: inventive 1.00:2.980 106 Pigment 93: inventive 1.00:2.980 105Pigment 94: inventive 1.00:2.980 103 Pigment 95: inventive 1.00:2.980105 Pigment 96: inventive  1.00:27.4286 103 Pigment 97: inventive 1.00:27.4286 105 Pigment 98: inventive  1.00:27.4286 105 Pigment 99:inventive  1.00:27.4286 104 Pigment 100: inventive  1.00:27.4286 104Pigment 101: noninventive  1.00:0.0317 99 Pigment 102: noninventive 1.00:0.0317 98 Pigment 103: noninventive  1.00:0.0317 97 Pigment 104:noninventive  1.00:0.0317 99 Pigment 105: noninventive  1.00:0.0317 95Pigment 106: noninventive  1.00:0.8571 94 Pigment 107: noninventive 1.00:0.8571 98 Pigment 108: noninventive  1.00:0.8571 99 Pigment 109:noninventive  1.00:0.8571 97 Pigment 110: noninventive  1.00:0.0317 96Pigment 111: noninventive 1.00:3.333 95 Pigment 112: noninventive1.00:3.333 98 Pigment 113: noninventive 1.00:3.333 99 Pigment 114:noninventive 1.00:3.333 96 Pigment 115: noninventive 1.00:3.333 97Pigment 116: noninventive 1.00:31.50 98 Pigment 117: noninventive1.00:31.50 96 Pigment 118: noninventive 1.00:31.50 98 Pigment 119:noninventive 1.00:31.50 96 Pigment 120: noninventive 1.00:31.50 97Pigment 121: noninventive  1.00:0.0294 100 Pigment 122: noninventive1.0:1.0  100 Pigment 123: noninventive 1.0:2.50 100 Pigment 124:noninventive 1.00:34.00 100 Pigment 125: noninventive  1.00:0.0241 100Pigment 126: noninventive  1.00:0.8889 100 Pigment 127: noninventive1.00:3.250 100 Pigment 128: noninventive 1.00:41.50 100 Pigment 129:noninventive  1.00:0.0333 100 Pigment 130: noninventive 1.00:0.860 100Pigment 131: noninventive  1.00:3.0435 100 Pigment 132: noninventive1.00:30.00 100 Pigment 133: noninventive  1.00:0.0543 100 Pigment 134:noninventive 1.00:0.940 100 Pigment 135: noninventive 1.00:2.880 100Pigment 136: noninventive 1.00:18.40 100 Pigment 137: noninventive 1.00:0.0365 100 Pigment 138: noninventive 1.00:0.990 100 Pigment 139:noninventive 1.00:2.980 100 Pigment 140: noninventive  1.00:27.4286 100Pigment 141: noninventive  1.00:0.0317 100 Pigment 142: noninventive 1.00:0.8571 100 Pigment 143: noninventive  1.00:3.3333 100 Pigment 144:noninventive 1.00:31.50 100

CONCLUSION

It is apparent from Table 1 that all the inventive pigments haveelevated colour strengths. This means that these pigments, based onequal starting weights, attain higher optical densities than thenoninventive pigments.

What is claimed is:
 1. Metal azo pigments comprising: a) at least threemetal azo compounds which differ at least in the type of metal and whicheach contain: structural units of the formula (I), or the tautomericforms thereof,

in which R¹ and R² are each independently OH, NH₂ or NHR⁵, R³ and R⁴ areeach independently ═O or ═NR⁵, and R⁵ is hydrogen or alkyl, and Ni²⁺ andCu²⁺ ions and at least one further metal ion Me, where: Me is a di- ortrivalent metal ion selected from the group consisting of La³⁺, Ce³⁺,Pr³⁺, Nd²⁺, Nd³⁺, Sm²⁺, Sm³⁺, Eu²⁺, Eu³⁺, Gd³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Yb²⁺,Yb³⁺, Er³⁺, Tm³⁺, Mg²⁺, Ca²⁺, Sr²⁺, Mn²⁺, Y³⁺, Sc³⁺, Ti²⁺, Ti³⁺, Nb³⁺,Mo²⁺, Mo³⁺, V²⁺, V³⁺, Zr²⁺, Zr³⁺, Cd²⁺, Cr³⁺, Pb²⁺ and Ba²⁺, the amountof Cu²⁺ and Ni²⁺ ions together is 70 to 99.5 mol % and the amount ofmetal ions Me is 30 to 0.5 mol %, based in each case on one mole of allmetal ions in the metal azo pigment, and the molar ratio of Cu²⁺ to Ni²⁺ions in the metal azo pigment is 42:1 to 1:42, and b) at least onecompound of the formula (II)

in which R⁶ is hydrogen or alkyl.
 2. The metal azo pigments according toclaim 1, wherein: R⁵ is hydrogen or C₁-C₄ alkyl; R⁶ is hydrogen, orC₁-C₄-alkyl, or C₁-C₄-alkyl mono- or polysubstituted by OH; and themolar ratio of Cu²⁺ to Ni²⁺ ions in the metal azo pigment is 10:1 to1:10.
 3. The metal azo pigments according to claim 2, wherein:components a) and components b) are present together in the form ofadducts; R¹ and R² are OH; R³ and R⁴ are ═O; and R⁶ is hydrogen; Me is ametal ion selected from the group consisting of La³⁺, Ce³⁺, Pr³⁺, Nd³⁺,Sm³⁺, Tb³⁺, Ho³⁺ and Sr²⁺; 1.0 to 2.0 mol of compounds of the formula(II) is present per mole of structural units of the formula (I); and thepigments have a specific surface area of 100 to 150 m²/g.
 4. The metalazo pigments according to claim 1, wherein components a) and componentsb) are present together in the form of adducts.
 5. The metal azopigments according to claim 1, wherein: R¹ and R² are OH, R³ and R⁴ are═O, and R⁶ is hydrogen.
 6. The metal azo pigments according to claim 1,wherein Me is a metal ion selected from the group consisting of La³⁺,Ce³⁺, Pr³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Yb³⁺, Er³⁺, Tm³⁺,Mg²⁺, Ca²⁺, Sr²⁺, Mn²⁺ and Y³⁺.
 7. The metal azo pigments according toclaim 1, wherein the pigments comprise 0.05 to 4 mol of compounds of theformula (II) per mole of structural units of the formula (I).
 8. Themetal azo pigments according to claim 1, wherein the pigments have aspecific surface area of 50 to 200 m²/g.
 9. The metal azo pigmentsaccording to claim 1, wherein the pigments produce an x-raydiffractogram wherein, at an interplanar spacing of d=12.2 (±0.2) Å,they have a signal S having an intensity I₁ which exceeds the backgroundvalue by 3 times the square root of this value.
 10. A process forproducing the metal azo pigments according to claim 1, the processcomprising contacting: a compound of the formula (III), or tautomersthereof,

in which X is an alkali metal ion, R¹ and R² are each independently OH,NH₂ or NHR⁵, R³ and R⁴ are each independently ═O or ═NR⁵, and R⁵ ishydrogen or alkyl, with at least one compound of the formula (II)

in which R⁶ is hydrogen or alkyl, either simultaneously or successivelywith at least one nickel salt, at least one copper salt, and at leastone further metal salt selected from the group consisting of the La³⁺,Ce³⁺, Pr³⁺, Nd²⁺, Nd³⁺, Sm²⁺, Sm³⁺, Eu²⁺, Eu³⁺, Gd³⁺, Tb³⁺, Dy³⁺, Ho³⁺,Yb²⁺, Yb³⁺, Er³⁺, Tm³⁺, Mg²⁺, Ca²⁺, Sr²⁺, Mn²⁺, Y³⁺, Sc³⁺, Ti²⁺, Ti³⁺,Nb³⁺, Mo²⁺, Mo³⁺, V²⁺, V³⁺, Zr²⁺, Zr³⁺, Cd²⁺, Cr³⁺, Pb²⁺ and Ba²⁺ salts,where 0.02 to 0.96 mol of at least one nickel salt, 0.02 to 0.96 mol ofat least one copper salt, and 0.005 to 0.3 mol of at least one metalsalt from the abovementioned group are used per mole of compound of theformula (III), and the sum total of the molar amounts of all the metalsalts is 100 mol %.
 11. The process according to claim 10, wherein: X isa sodium or potassium ion; R is hydrogen or C₁-C₄-alkyl; R⁶ is hydrogen,or C₁-C₄-alkyl mono- or polysubstituted by OH, and the at least onefurther metal salt is selected from the group consisting of La³⁺, Ce³⁺,Pr³⁺, Nd³⁺, Sm³⁺, Tb³⁺, Ho³⁺ and Sr²⁺ salts.
 12. Pigment preparationscomprising at least one metal azo pigment according to claim 1 and atleast one auxiliary and/or additive selected from the group consistingof surface-active agents, surface-covering agents, bases and solvents,and optionally at least one further pigment.
 13. The pigmentpreparations according to claim 12, further comprising C.I. PigmentGreen 36 and/or C.I. Pigment Green
 58. 14. A process for producing thepigment preparations according to claim 12, the process comprisingmixing or grinding the at least one metal azo pigment with at least oneauxiliary and/or additive selected from the group consisting of thesurface-active agents, the surface-covering agents, the bases andsolvents, and optionally the at least one further pigment.
 15. A colourfilter, photoresist, printing ink or liquid-crystal display comprisingthe at least one metal azo pigment according to claim
 1. 16. The colourfilter, photoresist, printing ink, or liquid-crystal display of claim15, wherein the at least one metal azo pigment is a component of apigment preparation comprising the at least one metal azo pigment and atleast one auxiliary and/or additive selected from the group consistingof surface active agents, surface-covering agents, bases and solvents,and optionally at least one further pigment.
 17. Photoresist comprisingat least one metal azo pigment according to claim 1, one or morephotocurable monomers, one or more reaction photoinitiators, andoptionally one or more binders or dispersants and/or solvents.
 18. Thephotoresist of claim 17, wherein the at least one metal azo pigment is acomponent of a pigment preparation comprising the at least one metal azopigment, and at least one auxiliary and/or additive selected from thegroup consisting of surface-active agents, surface-covering agents,bases and solvents, and optionally at least one further pigment.
 19. Aprocess for producing colour filters for liquid-crystal displays, theprocess comprising a) applying the photoresist according to claim 17 toa substrate, b) exposing the photoresist by means of a photomask, c)curing, and d) developing to provide a finished coloured colour filter.20. The metal azo pigments according to claim 1, wherein the molar ratioof Cu²⁺ to Ni²⁺ ions in the metal azo pigment is 3:1 to 1:3.